Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

Single chamber Solid Oxide Fuel Cells selective electrodes: A real chance with brownmillerite-based nanocomposites

In this contribution brownmillerite-based nanocomposite cathode for Single-Chamber Solid Oxide Fuel Cells is developed. These cells can be very attractive especially for small and cheap devices because of the absence of seals. The efficiency of SC-SOFCs is strictly connected to the selectivity of anode and cathode, the bottleneck for this technology. The development of a cathode inert in fuel oxidation is particularly challenging. Our strategy is to start from a catalytically un-active support (CFA = Ca₂FeAl_0.95Mg_0.05O₅) and induce the formation of iron oxide based nanoparticles, expected to activate oxygen. Symmetric (CFA + FeO_x/CGO/CFA + FeO_x) and complete cells (CFA + FeO_x/CGO/Ni-CGO) are studied in air and methane/oxygen 2:1 mixture. The Area Specific Resistance of CFA + FeO_x is less than 1/3 that of CFA. The high selectivity allows to reach an efficiency of 25%; power still needs to be increased but we demonstrated the possibility to develop selective low cost electrodes. The effect of air, methane/oxygen exposure and the heat treatments were carefully investigated.     

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.     

高分散度Pt/C电催化剂的制备

Cabot公司Vulcan XC-72型炭黑，经过H2O2氧化处理后作为Pt的载体，H2PtCl6作为金属前驱体制备了高度分散的Pt/C催化剂。讨论了不同条件下H2PtCl6在炭黑上的吸附性能。载体经过H2O2氧化处理24h,H2PtCl6在pH=9下吸收48h，H2 350℃还原2h，可以制备出铂晶粒平均大小为1.8nm的Pt/C电催化剂。     

氧化钙固体碱催化剂用于大豆油和甲醇酯交换制备生物柴油的研究

对氧化钙固体碱催化剂用于甲醇和大豆油的酯交换反应制备生物柴油（脂肪酸甲酯）进行了研究，考察了醇油摩尔比、反应温度、催化剂用量等因素对生物柴油产率的影响，以及采用四氢呋喃等溶剂溶解产物中的甘油和脂肪酸甲酯以分离回收催化剂的方法。结果表明，在醇油摩尔比为12、反应温度为65℃、催化剂用量为8％、反应1．5h的条件下，生物柴油产率达到了95％以上。重复使用实验结果表明，CaO的催化活性比K2CO3／γ-Al2O3和KF／γ-Al2O3固体碱催化剂高，寿命更长，重复使用20次后催化效果无明显下降。     

Synthesis of amphiphilic magnetic microspheres by dispersion copolymerization of styrene and poly(ethylene oxide) macromonomer

Amphiphilic magnetic microspheres ranging in diameter from 5 to 100 µm were prepared by dispersion copolymerization of styrene and poly(ethylene oxide) vinylbenzyl (PEO‐VB) macromonomer (MPEO) in the presence of Fe₃O₄ magnetic fluid. The effects of various polymerization parameters on the average particle size were systematically investigated. The average particle size was found to increase with increasing styrene concentration and initiator concentration. It also increased with decreasing stabilizer concentration and molecular weight of MPEO. The content of the hydroxyl groups localized in the microspheres ranged from 0.01 to 0.2 mmol g^?1. © 2003 Society of Chemical Industry     

色散补偿及EDFA增益均衡的一体化

提出一种新的色散补偿及EDFA增益均衡的一体化方法。在10Gb／s的光通信系统和600km G652光纤中首次实现了基于16个碉啾光纤布拉格光栅(FBG)的色散补偿及掺饵光纤放大器(EDFA)的增益均衡。16个FBG的波长间隔为1．6nm，波长覆盖C波段1529～1556nm约27nm的范围。经600km G652光纤传输后，10Gb／s的NRZ码传输功率代价小于2dB。     

MD膜驱剂的粘土稳定性研究Ⅰ.静态试验

粘土的膨胀和分散是引起地层伤害的两个重要因素。通过测定Zeta电位、XRD、悬浮液透光率、FT-IR考察了MD膜驱剂（MDFFA）对粘土稳定性的作用。结果表明，MDFFA的浓度低于0．3 mmol／g（以蒙脱土质量计）时，蒙脱土悬浮液Zeta电位的提高是由于膜驱剂分子的吸附改变了蒙脱土的层电荷；高于此浓度时，Zeta电位进一步提高是由于双电层的压缩。随着MDFFA浓度的增大，蒙脱土的完全膨胀层向部分膨胀层转化，并且经水冲洗、浸泡后，其XRD谱峰位置变化不大。较高浓度的MDFFA，能有效地抑制蒙脱土的分散，且不会形成对地层有害的絮凝体。MDFFA使蒙脱土层间水的含量明显降低。     

波动方程数值模拟的隐式差分法

在有限差分波动方程数值模拟中,通常采用高阶差分方法来提高空间导数的数值逼近精度,以实现降低数值频散,提高数值模拟精度的目的。首先对差分频散进行了理论分析;然后讨论了估计一阶空间导数的隐式差分格式,并与通常采用的高阶精度显式差分格式进行了对比分析,结果表明,隐式差分格式能够在更宽的波数范围使差分频散控制在可接受的水平,如8阶精度的显式差分格式所适应的波数带宽约为O．55kmax,而隐式差分格式所适应的波数带宽约为0．7kmax;最后通过模型试算,对隐式差分格式的有效性进行了验证。模拟结果表明,用隐式差分格式在一定程度上降低了差分频散,提高了模拟精度。     

T-ZnO晶须增强环氧树脂复合材料的力学行为

研究了以四脚状氧化锌（T-ZnO）晶须为增强剂，环氧树脂复合材料的力学行为。结果表明，由具有三维空间结构的T-ZnO晶须为增强剂所制备的环氧树脂复合材料具有各向同性的力学性能，T-ZnO晶须填加质量分数为6%时，就可使材料的力学性能改善；拉伸强度提高到169%，拉伸功几乎提高了100%，冲击强度提高到300%，抗弯的断裂功提高到158%，而压缩强度略有下降。