Reduction of NO2 stored in a commercial lean NO x trap at low temperatures

Isothermal storage of NO₂ and subsequent reduction with different reducing agents (H₂, CO or H₂ + CO) in a lean NO _x trap catalyst was tested by Temperature Programmed Desorption (TPD) and Temperature Programmed Reduction (TPR) experiments at temperatures representative of automotive “cold-start” conditions (<200 °C) using a commercial NO _x trap catalyst. Results from the TPR experiments revealed that no reduction of stored NO₂ to N₂ was observed at 100–180 °C, and at 200 °C 10% reduction only of NO₂ to N₂ was measured. A special affinity of H₂ to form NH₃ was observed during the reduction of stored NO₂. The formation of NH₃ increases with increasing amount of stored NO₂ and decreases with increasing storage temperature. Direct relation exists between the amount of adsorbed and/or stored NO₂ and the formation of H₂O and NH₃.     

羟胺催化臭氧降解邻苯二甲酸甲酯

利用硫酸羟胺（HAS）催化臭氧（O3）降解含有邻苯二甲酸二甲酯（DMP）的模拟废水,比较O3/HAS体系和O3体系中DMP的降解情况,研究了叔丁醇（TBA）和pH值对O3/HAS体系中O3分解的影响。结果表明：当pH=3.0且HAS初始浓度为20μmol/L时,反应5min后O3/HAS体系中DMP的降解率比O3体系中提高了82.58%,表明O3/HAS体系降解DMP的效率优于单独O3体系;加入TBA后O3/HAS体系对DMP的降解率显著下降,证明在O3/HAS体系中产生了羟基自由基;在pH值为3.0、7.0和9.2的条件下,O3的降解率均随着HAS浓度的升高而升高,说明HAS促进了O3的分解。此外,选择盐酸羟胺（HAC）、磷酸羟胺（HAP）催化O3降解DMP,将O3/HAS体系、O3/HAC体系、O3/HAP体系中DMP的去除效果进行对比,结果显示三种体系均可促进DMP的降解。     

Effects of ion group content and polyol molecular weight on physical properties of HTPB‐based waterborne poly(urethane‐urea)s

A series of waterborne poly(urethane‐urea)s, WPUUs, based on using nonpolar hydroxyl‐terminated polybutadiene (HTPB) as the soft segment, were successfully synthesized in this article. The effects of the COOH group content and soft‐segment molecular weight (Mn_s) on the dispersion, morphology, and physical properties were investigated. Variations of the particle size, viscosity, and zeta potential were first governed by the hydrophilicity of the polymer chain, and then by the swelling derived from water. Fourier transfer infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) indicated that the degree of phase separation decreased as the COOH group content increased or as Mn_s decreased. However, the hydrogen bonding between the soft and hard segments and the two‐phase mixing could not occur in this nonpolar HTPB‐based WPUU system, indicating that the hard segments tended to form smaller domains and to pack more loosely. It was attributed to the fact that the presence of bulky ionic salt groups destroyed the ordered arrangement of the hard segments. In this case, the increases of the interface area between the soft and hard phases resulted in that the present behaviors were similar to the phase mixing. In tensile properties, HTPB‐based WPUUs exhibited higher tensile stress, elongation at break, and modulus as the COOH group content decreased or as Mn_s decreased. In thermal degradation, the introduction of HTPB polyol improved the thermal stability of WPUU. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Interaction of methane with surfaces of silica,aluminas and HZSM-5 zeolite. A comparative FT-IR study

Infrared investigations on the interaction of methane with silica, aluminas (, and ) and HZSM-5 zeolite have been carried out. At low temperature (173 K), methane adsorption was observed over these oxides and HZSM-5 zeolite. Our findings featured that the infrared inactive ₁ band (2917 cm^–1) of a gaseous methane molecule became active and shifted to lower frequencies (2900 and 2890 cm^–1) when it adsorbed on the surfaces of these adsorbents. Our results also demonstrate that hydroxyl groups played a very important role in methane adsorption over the acidic oxides and the HZSM-5 zeolite. When interaction between the hydroxyl groups and methane took place, the band shift of the hydroxyl groups varied with different oxides. The strength of the interaction decreased according to the following sequence, Si-OH-Al>Al-OH>Si-OH, which is in accordance with the order of their acidities. At higher temperatures, methane interacted quite differently with various oxides and HZSM-5 zeolite. It has been observed that the hydroxyl groups of silica, -alumina and HZSM-5 zeolite could exchange with CD₄ at temperatures higher than 773K, while those on -alumina could exchange at a temperature as low as 573 K. Another interesting observation was the formation of formate species over Al₂O₃ (both and ) at temperatures higher than 473 K. The formate species would decompose to CO₂, or produce carbonate at much higher temperatures. Formation of formate species was not observed over silica and HZSM-5 under similar conditions, -Al₂O₃ did not adsorb or react with methane in any case.     

超高交联树脂吸附对硝基苯乙酮和对硝基苯甲酸的研究

研究了NDA-150、NDA-99、NDA-88、Amberlite XAD-4．4种吸附树脂对对硝基苯乙酮和对硝基苯甲酸的静态吸附行为。结果表明NDA—150树脂对硝基化合物的吸附效果较好。并研究NDA-150树脂的动态吸附和脱附行为．结果显示：NDA-150树脂对对硝基苯甲酸的吸附容量为2．32mmol／g干树脂，对对硝基苯乙酮的吸附容量为3．06mmol／g干树脂。NDA—150树脂易于脱附，吸附对硝基苯甲酸后．用2％NaOH：乙醇(体积比1：1)作脱附剂，温度313K；吸附对硝基苯乙酮后，用甲醇作脱附剂，温度333K，体积6BV，脱附率均接近100％。     

Time-of-flight studies on catalytic model reactions

Time-of-flight spectroscopy (TOF) and REMPI-TOF (resonance enhanced multi-photon ionization-TOF) were applied to measure the angular and translational energy distribution, as well as the internal state resolved energy distribution of desorption and reaction products on some model systems. Desorption of hydrogen and deuterium from clean and modified Pd(111) surfaces was studied, where the palladium sample was part of a permeation source. Water formation by reaction of oxygen with hydrogen on palladium was investigated by using different types of hydrogen supply: molecular H₂ exposure and atomic H exposure from the gas phase, as well as H exposure by permeating hydrogen. Vanadium oxide nanostructures on Pd(111) were prepared and the influence on D₂ desorption and D₂O production was investigated with the permeation technique. Additionally, deuterium desorption from sulfur and oxygen covered V(111) and V(100) surfaces was studied by TOF and REMPI-TOF spectroscopy. From the TOF spectra information concerning the reaction and desorption dynamics (activation barriers) could be gained.     

TiO2／UV／O2和TiO2／UV／N2体系降解水中对氯硝基苯

以商用TiO2P25为催化剂,分别在TiO2/UV/O2和TiO2/UV/N2两种体系下进行降解对氯硝基苯(pCNB)试验.采用ESR对两种体系下光催化反应形成的.OH进行测定,利用LC-MS对两种体系下反应形成的中间产物进行了定性和定量分析,最后对pCNB降解过程中氯和硝基的存在形式进行了研究.结果表明:TiO2/UV/O2体系的催化降解效果要明显优于TiO2/UV/N2体系;两种反应体系都有.OH产生,并且TiO2/UV/O2体系产生的.OH的量多于TiO2/UV/N2体系产生的.OH的量;TiO2/UV/O2体系形成的中间产物的种类要多于TiO2/UV/N2体系形成的,苯环上的氢、氯、硝基均可被.OH取代形成对硝基酚(pNP)、5-氯-2-硝基酚(5-C-2-PN)等酚类物质;两种体系下均有Cl-和NO2-存在,其中Cl-生成势与pCNB的去除势一致,只有TiO2/UV/O2体系中存在NO3-.     

Plasma desorption mass spectrometry, an analytical tool in protein engineering: characterization of modified insulins

Californium-252 plasma desorption mass spectrometry (PDMS) hasbeen employed for the characterization of a series of humaninsulin derivatives in order to evaluate the performance ofthis technique as an analytical tool in protein engineering.Several of the characterized modifications result in a 1 a.m.u.mass change. The precision in mass determination obtainableby PDMS analysis is not sufficient for unambiguous verificationof such modifications based on the molecular weight alone. Itis, however, possible to carry out in situ enzymatic digestionof the sample. Subsequent PDMS analysis will in most cases revealif the modification has been introduced as intended.     

复合型调湿涂料的研制及实验研究

将硅藻土做成乳胶型涂料，并得到了不同湿度下这种涂料的吸放湿性能曲线，但是吸放湿能力不是很理想。为了提高涂料的吸放湿能力，在基料中加入无机成膜物质制成硅藻土复合涂料，结果表明，通过复合，最大吸湿能力从6．5％提高到11％，最大放湿能力从5％提高到10％，并且确定了无机成膜物质的比例。复合涂料符合建筑涂料的常规性能要求，在调节湿度的同时克服了传统空调能耗高的缺点，具有很好的应用前景。