Low-temperature adsorption/storage of hydrogen on FAU, MFI, and MOR zeolites with various Si/Al ratios: effect of electrostatic fields and pore structures

Several zeolites, such as faujasite, mordenite, and ZSM-5, with various aluminum contents have been used to analyze the effect of aluminum or cation concentration (strength of electrostatic field) on hydrogen adsorption at low temperature. Irrespective of the zeolite structure, the adsorption capacity, isosteric heat of adsorption (-DeltaHads), surface coverage, and micropore occupancy increase with increasing aluminum content of a zeolite. Zeolites with a higher amount of aluminum favorably adsorb hydrogen at relatively low pressures. For zeolites with similar aluminum contents, the adsorption capacity, isosteric heat of adsorption, surface coverage, and micropore occupancy are in the order of mordenite>ZSM-5>faujasite, probably due to differing pore sizes and the presence or absence of pore intersections. This work demonstrates that zeolites with strong electrostatic fields and narrow pores without intersections are beneficial for high hydrogen uptake.     

水发泡淀粉挤出泡沫的结构与性能

以水为发泡剂,普通玉米淀粉为原料,采用双螺杆挤出机制备淀粉泡沫材料,研究了发泡剂用量及聚乙烯醇的加入量对泡沫材料结构与性能的影响。 用扫描电子显微镜观察了泡沫材料截面的形态,用万能材料试验机测试了泡沫材料的力学性能。 结果表明,水的质量分数为8%时淀粉泡沫径向膨胀率和发泡倍率最高,分别为22倍和17.6倍,压缩模量最高（4.07 MPa）。 加入质量分数10%的聚乙烯醇(PVA)使淀粉泡沫的孔径变大至1.29 mm,壁厚增加至82.43 μm,同时压缩模量增加至9.70 MPa。     

Al_2O_3包覆Ba_(0.6)Sr_(0.4)TiO_3复合粉体制备及表征

采用液相包覆法制备了Al2O3包覆的Ba0.6Sr0.4TiO3复合粉体。通过SEM,TEM,TG-DSC,XRD,XPS和ζ电位测试对包覆前后粉体的表面形貌、组织结构、等电点进行了测试和分析。结果表明:Al2O3以无定形结构成功的包覆在Ba0.6Sr0.4TiO3粉体表面,形成了Ba-O-Al、Sr-O-Al和Ti-O-Al键,Ba0.6Sr0.4TiO3颗粒的等电点由包覆前的pH=3.2增大至pH=8。     

Structure of Framework Aluminum Lewis Sites and Perturbed Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR (3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics

Zeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework Al_FR Lewis acid sites are often found in their H‐forms. The formation of Al_FR Lewis sites in zeolites is a key issue regarding their selectivity in acid‐catalyzed reactions. The local structures of Al_FR Lewis sites in dehydrated zeolites and their precursors—“perturbed” Al_FR atoms in hydrated zeolites—were studied by high‐resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)₃AlOH groups and are characterized by a broad ²⁷Al NMR resonance (δ_i=59–62 ppm, C_Q=5 MHz, and η=0.3–0.4) with a shoulder at 40 ppm in the ²⁷Al MAS NMR spectrum. Dehydroxylation of (SiO)₃AlOH occurs at mild temperatures and leads to the formation of Al_FR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)₃Al Lewis sites exhibit an extremely broad ²⁷Al NMR resonance (δ_i≈67 ppm, C_Q≈20 MHz, and η≈0.1).     

Fluorine plasma treatment of bare and nitrilotris(methylene)triphosphonic acid (NP) protected aluminum: an XPS and ToF‐SIMS study

Nitrilotris(methylene)triphosphonic acid (NP) is a technologically important molecule that has been used for years as a corrosion inhibitor and/or adhesion promoter on aluminum and other metal surfaces. However, to the best of our knowledge, the detailed surface characterization of NP adsorbed on aluminum, or on any other surface, has not been reported. Herein, we report an X‐ray photoelectron spectroscopy and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) analysis of a series of untreated and NP‐coated aluminum substrates that were exposed to the downstream products of a fluoroalkane + oxygen plasma for different amounts of time (from 0 to 20 s). As indicated by P 2p, N 1s, Al 2p, O 1s, and F 1s narrow scans, even a 4‐s plasma treatment significantly damages the NP protective layer and converts the native aluminum oxide into aluminum oxyfluoride. Heat treatment of the fluorine plasma‐treated samples in the air substantially converts the aluminum oxyfluoride back to aluminum oxide, while similar heating under vacuum results in little change to the materials. A slow loss of fluorine from the samples occurs over the course of weeks when they are stored in the air. A ToF‐SIMS analysis reveals sets of signals that are consistent with no surface treatment, NP treatment, or fluorine plasma treatment. A principal component analysis of the negative ion ToF‐SIMS spectra from the samples shows the expected differentiation of the samples. Copyright © 2014 John Wiley & Sons, Ltd.     

Fe K‐Edge X‐ray Absorption Fine Structure Determination of γ‐Al2O3‐Supported Iron‐Oxide Species

The structure of FeO_x species supported on γ‐Al₂O₃ was investigated by using Fe K‐edge X‐ray absorption fine structure (XAFS) and X‐ray diffraction (XRD) measurements. The samples were prepared through the impregnation of iron nitrate on Al₂O₃ and co‐gelation of aluminum and iron sulfates. The dependence of the XRD patterns on Fe loading revealed the formation of α‐Fe₂O₃ particles at an Fe loading of above 10 wt %, whereas the formation of iron‐oxide crystals was not observed at Fe loadings of less than 9.0 wt %. The Fe K‐edge XAFS was characterized by a clear pre‐edge peak, which indicated that the Fe?O coordination structure deviates from central symmetry and that the degree of Fe?O?Fe bond formation is significantly lower than that in bulk samples at low Fe loading (<9.0 wt %). Fe K‐edge extended XAFS oscillations of the samples with low Fe loadings were explained by assuming an isolated iron‐oxide monomer on the γ‐Al₂O₃ surface.     

Dynamic mechanical properties of aluminum nitride/cyanate ester composites for high performance electronic packaging

Viscoelastic ature is one of the key features of polymeric composites. A series of cyanate ester (CE)‐based composites with different aluminum nitride (AlN) contents for high performance electronic packaging, coded as AlN/CE, were developed; the viscoelastic nature of AlN/CE composites was intensively investigated by employing dynamic mechanical analysis (DMA). Results show that the AlN content has a great effect on dynamic mechanical properties of AlN/CE composites. The storage modulus in the glassy region increases linearly with the addition of AlN as well as the increase of AlN content. Meanwhile, all composites also exhibit notably higher loss modulus than cured CE resin due to the appearance of new energy dissipation forms. In addition, the incorporation of AlN has a significant effect on damping factor peak. All reasons leading to these phenomena are analyzed from the view of structure–property relationship. Copyright © 2009 John Wiley & Sons, Ltd.     

天然CXN沸石分子筛水热稳定性研究 II. 水蒸汽处理温度对铵型沸石物化性质的影响

在前文研究天然Stilbite沸石(CXN沸石)水热稳定性影响因素的基础上, 以27Al与29Si MAS NMR, NH3-TPD和低温氮吸附等详细研究了铵型CXN沸石骨架铝配位状态和硅配位状态, 表面酸性与孔性质等与水蒸汽处理温度的关系. 随温度升高, 沸石骨架硅铝比逐渐提高, 并伴随硅羟基缺陷增多. 经750 ℃水蒸汽处理3 h后沸石骨架硅铝比可达到21.3. 沸石总酸量随水蒸汽处理温度的提高而降低, 沸石骨架铝脱除造成沸石孔道部分被堵塞, 但同时形成有利于分子扩散的介孔.     

Planar or quasi-planar octa- and ennea-coordinate aluminum and gallium in boron rings

An ab initio theoretical investigation has been performed on planar or quasi-planar octa-and ennea-coordinate Al and Ga centered in X@B8- and X@B9 (X=Al, Ga). These high symmetry molecular wheels all turned out to be true minima of the systems and σ+π double aromatic in nature, similar to the previously characterized D8h B@B8- both electronically and geometrically. Adiabatic and vertical detachment energies of the anions and the ionization potentials of the neutrals have been calculated to aid their eventua...