CO selective methanation in hydrogen-rich gas mixtures over carbon nanotube supported Ru-based catalysts

Series of carbon nanotube supported Ru-based catalysts were prepared by impregnation method and applied successfully for complete removal of CO by CO selective methanation from H2-rich gas stream conducted in a fixed-bed quartz tubular reactor at ambient pressure.It was found that the metal promoter,reduction temperature and metal loading affected the catalytic properties significantly.The most excellent performance was presented by 30 wt% Ru-Zr/CNTs catalyst reduced at 350℃.Since it decreased CO concentration to below 10ppm from 12000ppm by CO selective methanation at the temperature range of 180-240℃,and kept CO selectivity higher than 85% at the temperature below 200℃.Characterization using XRD,TEM,H2-TPR and XPS suggests that Zr modification of Ru/CNTs results in the weakening of the interaction between Ru and CNTs,a higher Ru dispersion and the oxidization of surface Ru.Amorphous and high dispersed Ru particles with small size were obtained for 30 wt% Ru-Zr/CNTs catalyst reduced at 350℃,leading to excellent catalytic performance in CO selective methanation.     

Self-supported interconnected Pt nanoassemblies as highly stable electrocatalysts for low-temperature fuel cells

In it for the long haul: Clusters of Pt nanowires (3D Pt nanoassemblies, Pt?NA) serve as an electrocatalyst for low-temperature fuel cells. These Pt nanoassemblies exhibit remarkably high stability following thousands of voltage cycles and good catalytic activity, when compared with a commercial Pt?catalyst and 20?%?wt Pt?catalyst supported on carbon black (20?% Pt/CB).     

Probing the electronic structure and chemical bonding of the "staple" motifs of thiolate gold nanoparticles: Au(SCH3)2- and Au2(SCH3)3-

Thiolate-protected gold nanoparticles have been found recently to be coordinated by the so-called "staple" bonding motifs, consisting of quasi-linear [RS-Au-SR] and V-shaped [RS-Au-(SR)-Au-SR] units, which carry a negative charge formally. Using photoelectron spectroscopy (PES) in conjunction with ab initio calculations, we have investigated the electronic structure and chemical bonding of the simplest staples with R = CH(3): Au(SCH(3))(2)(-) and Au(2)(SCH(3))(3)(-), which were produced by electrospray ionization. PES data of the two Au-thiolate complexes are obtained both at room temperature (RT) and 20 K. The temperature-dependent study reveals significant spectral broadening at RT, in agreement with theoretical predictions of multiple conformations due to the different orientations of the -SCH(3) groups. The Au-S bonds in Au(n)(SCH(3))(n+1)(-) (n = 1, 2) are shown to be covalent via a variety of chemical bonding analyses. The strong Au-thiolate bonding and the stability of the Au-thiolate complexes are consistent with their ubiquity as staples for gold nanoparticles and on gold surfaces.     

Sensitive detection of H(2)O(2) and H(2)O(2)-related reactant with Ru(bipy)(2)(7,8-dimethyl-dipyridophenazine)(2+) and oligodeoxyribonucleotide

A sensor for H(2)O(2) and H(2)O(2)-related reactant was constructed with oligonucleotides and Ru(bipy)(2)dppx(2+) (bipy = 2,2'-bipyridine, dppx = 7,8-dimethyl-dipyridophenazine), which was performed by converting the H(2)O(2)-induced DNA cleavage into the change of luminescence. The 'DNA light switch' Ru(bipy)(2)dppx(2+) could emit strong luminescence in the presence of dsDNA. DNA cleavage occurred upon addition of H(2)O(2) due to the Fenton reaction, which resulted in the decrease of the luminescence of Ru(bipy)(2)dppx(2+). Therefore, the luminescence intensity depended on the concentration of H(2)O(2) and H(2)O(2)-related reactants, and the detection limits for H(2)O(2), uric acid and cholesterol were 0.20 μM, 0.46 μM and 1.25 μM, respectively. The recovery varied between 94.0% and 105.0% when the assay was applied to the determination of uric acid and cholesterol in biological samples, which demonstrated the good practicability of the assay.     

Carbon‐Decorated Single‐Crystalline Ni2P Nanotubes Derived from Ni Nanowire Templates: A High‐Performance Material for Li‐Ion Batteries

Single‐crystalline Ni₂P nanotubes (NTs) were facilely synthesized by using a Ni nanowire template. The mechanism for the formation of the tubular structures was related to the nanoscale Kirkendall effect. These NTs exhibited a core/shell structure with an amorphous carbon layer that was grown in situ by employing oleylamine as a capping agent. Galvanostatic charge/discharge measurements indicated that these Ni₂P/C NTs exhibited superior high‐rate capability and good cycling stability. There was still about 310 mAh g^?1 retained after 100 cycles at a rate of 5 C. Importantly, the tubular nanostructures and the single‐crystalline nature of the Ni₂P NTs were also preserved after prolonged cycling at a relatively high rate. These improvements were attributed to the stable nanotubular structure of Ni₂P and the carbon shell, which enhanced the conductivity of Ni₂P, suppressed the aggregation of active particles, and increased the electrode stability during cycling.     

Comparing microcrystalline with spherical nanocrystalline cellulose from waste cotton fabrics

Microcrystalline cellulose (MCC) and spherical nanocrystalline cellulose (SNCC) were successfully prepared from waste cotton fabrics through acid hydrolysis. The comparative analysis of the morphology and structure between the obtained MCC and SNCC was carried out. The SNCC suspension exhibited higher stability than the MCC suspension. Transmission electron microscopy in combination with atomic force microscopy showed that the cellulose nanospheres with average size of 35?nm were achieved, while the average particle size of MCC was 49?μm. The MCC and SNCC had similar functional groups and crystalline structure as confirmed by Fourier transform infrared spectroscopy and X-ray diffraction analysis, respectively. Viscometric average molecular weight measurement and thermo gravimetric analysis indicated that the degree of polymerization and thermal stability of SNCC was lower than that of MCC. These results should improve understanding of the characteristics of MCC and SNCC derived from waste cotton fabrics and lead to many new applications.     

GMA和共单体对聚乙烯木塑复合材料的直接反应增容

通过甲基丙烯酸缩水甘油酯(GMA)、聚乙烯(PE)、木粉和其它助剂的熔融挤出,实现了GMA及GMA与共单体对PE和木粉的直接反应增容.通过扫描电镜(SEM)观测了PE基木塑复合材料(WPC)的冲击断面形貌.测试了WPC经抽提后所得木粉的傅立叶变换红外光谱(FTIR)和WPC的力学性能及热变形温度(HDT).研究了共单体苯乙烯(St)和抑交联剂亚磷酸三苯酯(TPP)对反应增容的影响.结果显示,经GMA和引发剂反应增容后,有部分PE分子键合到了木粉粒子上,从而增强了木塑两相的结合力;St的加入有利于提高GMA的接枝率,导致更多PE分子键合到了木粉粒子上,而TPP的加入则使GMA的接枝率有所下降.经GMA和引发剂直接反应增容后,WPC的力学性能和HDT均明显改善;St的加入有助于抑制PE的交联,但并未造成WPC力学性能和HDT的明显劣化;同时加入St和TPP后,WPC的HDT有所下降,而断裂伸长率和冲击强度则明显提高.     

La15Fe77B8型储氢合金的结构和电化学性能

研究了快淬和退火态La15Fe77B8型储氢合金的组织结构和电化学性能。应用中频感应熔炼-快淬方法制备了La15Fe77B8型储氢合金,其组成为La15Fe2Ni72Mn7B2Al2。结构分析表明:快淬La15Fe2Ni72Mn7B2Al2合金为多相结构,包括LaNi5相、La3Ni13B2相和(Fe,Ni)相,快淬合金经1223 K保温3 h,然后在873 K保温3 h退火处理后,LaNi5相增加,La3Ni13B2相几乎消失,(Fe,Ni)相增加且形态变大。电化学测试表明,退火合金的最大容量(307 mAh.g-1)略小于快淬合金(309 mAh.g-1),而循环稳定性有所改善。退火合金电极的倍率放电能力(HRD)低于快淬合金,原因在于交换电流密度(I0)及氢在合金中的扩散系数(D)降低。快淬和退火合金电极在低温233 K时均能放出55%的容量。     

活性炭基Li2SO4水系电解液超级电容器

采用中性Li2SO4水溶液代替H2SO4和KOH作为电解液制备了活性炭(AC)基对称型超级电容器,使水系超级电容器的工作电压由1.0V提高到了1.6V.采用循环伏安和充放电测试研究了电容器的稳定电化学窗口.电化学充放电测试表明电容器在0.25A.g-1电流密度下单电极比容量可达129F.g-1,在功率密度为160W.kg-1时能量密度达到10Wh.kg-1(以正负极活性物质的总质量计).1.6V恒压充电1h后电容器漏电流为0.22mA.超级电容器的库仑效率接近100%,充放电循环5000次后容量仍可保持在92%以上.研究了电解液的浓度对电容器电化学性能的影响,发现随着Li2SO4浓度的增大电容器的电荷转移电阻显著减小,大电流充放电性能提高.活性炭基Li2SO4水系电解液超级电容器具有工作电压高、能量密度高和对环境友好等优点,因此有很好的产业化前景.     

Studies of the g factors and the local structure of the orthorhombic Ni center in KTaO3 crystal

The local structure and the g factor (g_x, g_y, and g_z) of the Ni⁺ center in KTaO₃ are theoretically studied using the perturbation formulas of the g factors for a 3d⁹ ion in orthorhombically elongated octahedra. The orthorhombic field parameters are determined from the superposition model and the local geometry of the system. In view of the covalency, the contributions from the ligand orbital and spin–orbit coupling interactions are taken into account from the cluster approach. In the calculations, the orthorhombic center is attributed to Ni⁺ occupying the host Ta⁵⁺ site, associated with the nearest-neighboring oxygen vacancy V_O along the c-axis. Furthermore, the planar Ni⁺–O²⁻ bonds are found to experience the relative variation ΔR (≈0.076 Å) along the a- and b-axis, respectively, due to the Jahn–Teller effect and the size mismatching substitution of Ta⁵⁺ by Ni⁺. Meanwhile, the effectively positive V_O can make the central Ni⁺ displace away from V_O along the c-axis by about 0.20 Å. The calculated g factors based on the above local distortions show good agreement with the experimental data.