Assessing contaminated hydrogen peroxide for safe storage and transportation using the FTAI

Hydrogen peroxide is a very versatile oxidizing agent, and it is also environmentally compatible considering that the products of its exothermic decomposition are oxygen and water.When kept in a clean temperature-controlled environment, the self-reaction (decomposition) rate is extremely low. However, it is well known that even a small amount of contamination will dramatically increase the reaction rate. This paper describes the use of the fast thermal activity interpreter (FTAI) instrument to examine the chemical reactivity of commercially available 50% hydrogen peroxide at two different temperatures (30 and 40°C) both with and without contamination. The results show that at 30°C a small amount of rust (330 ppm) increases the reaction rate of 50% hydrogen peroxide by a factor of 50. When the temperature is increased to 40°C, the reaction rate is further increased by almost a factor of four. The implication for reactivity management is that at this contamination level most practical vessel sizes would require emergency venting capability. An evaluation was then performed to determine the emergency venting requirement for the safe transportation or storage of the contaminated hydrogen peroxide. It was determined that for quantities of the material less than 5 gallons, conventional breather vents would be sufficient to accommodate the gas evolved. However, for larger quantities, a safety relief device would be needed. For example, for a 400-gallon tote bin at 40°C the required minimum vent area is estimated to be 4.3 in², corresponding to a minimum vent diameter of 2.3 inches.     

硼的添加对Ti0.26Zr0.07V0.24Mn0.1Ni0.33贮氢合金结构和电化学性能的影响

Ti0.26Zr0.07V0.24Mn0.1Ni0.33Bx(x=0~0.10)系列合金均有V基固溶体相和C14型Laves相两相组成。添加B可提高Ti0.26Zr0.07V0.24Mn0.1Ni0.33合金的放电容量,Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.1合金电极在60 mA·g-1电流放电时的放电容量达到476.7 mAh·g-1。B的添加不同程度地降低了合金的高倍率放电性能,使合金电极表面上电化学反应的电荷转移电阻(R ct)显著增加,交换电流密度(I0)显著降低。添加B可显著改善Ti0.26Zr0.07V0.24Mn0.1Ni0.33合金电极的高温放电性能,Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.025合金电极在343 K高温下其放电容量达到525.6 mAh·g-1。     

碳化硅和碳化硼在电催化中的应用

燃料电池是具有广泛应用前景的新能源技术。碳载铂基催化剂（Pt/C）是最常用的燃料电池电极催化剂,不过Pt/C稳定性较差、且成本高昂,严重限制了燃料电池的规模化应用。共价型碳化物碳化硅和碳化硼,由于具有极强的共价键,其物化稳定性优异,成为制备高稳定性、低成本的燃料电池催化剂的重要基础材料。本文总结了相关研究成果,介绍了碳化硅和碳化硼的独特优势,讨论了相关研究的发展方向。     

Gas storage of simple molecules in boron oxide nanocapsules

The capability of the B₂₀O₃₀ nanocapsule to store H₂, N₂, CO, CO₂, NH₃, CH₄, and Cl₂ molecules on the outer surface and inside of the cage was investigated using Monte Carlo simulations, long‐range and dispersion corrected density functional theory, and Møller–Plesset second‐order perturbation theory. Also, Monte Carlo simulations were employed to investigate the adsorption behavior of larger number of guest molecules inserted into and onto the larger B₈₀O₁₂₀ and B₂₀O₃₀@B₈₀O₁₂₀ cages. Absolute localized molecular orbitals energy decomposition analysis was used to describe the nature of intermolecular interactions in these endohedral and exohedral complexes. It is found that the hydrogen and ammonia gases are diffused to the inside of spherical B₂₀O₃₀ capsule, while other guest molecules prefer to interact with the outer surface of spherical and pyramidal capsules. For B₈₀O₁₂₀, up to 26 H₂ and 11–14 N₂, CO, CO₂, NH₃, and CH₄ molecules are stored inside the capsule. The residual molecules are adsorbed on the outer surface of nanocapsule. © 2013 Wiley Periodicals, Inc.     

Polymer/boron nitride nanocomposite materials for superior thermal transport performance

Boron nitride nanosheets were dispersed in polymers to give composite films with excellent thermal transport performances approaching the record values found in polymer/graphene nanocomposites. Similarly high performance at lower BN loadings was achieved by aligning the nanosheets in poly(vinyl alcohol) matrix by simple mechanical stretching (see picture).     

硼的添加对Ti0.26Zr0.07V0.24Mn0.1Ni0.33贮氢合金结构和电化学性能的影响

Ti_0.26Zr_0.07V_0.24Mn_0.1Ni_0.33Bx(x=0~0.10)系列合金均有V基固溶体相和C14型Laves相两相组成。添加B可提高Ti_0.26Zr_0.07V_0.24 Mn_0.1Ni_0.33合金的放电容量, Ti_0.26Zr_0.07V_0.24Mn_0.1Ni_0.33B0.1合金电极在60 mA·g^-1电流放电时的放电容量达到476.7 mAh·g^-1.B的添加不同程度地降低了合金的高倍率放电性能, 使合金电极表面上电化学反应的电荷转移电阻(R_ct)显着增加, 交换电流密度(I₀)显着降低。添加B可显着改善Ti_0.26Zr_0.07V_0.24Mn_0.1Ni_0.33合金电极的高温放电性能, Ti_0.26Zr_0.07V_0.24Mn_0.1Ni_0.33B_0.025合金电极在343 K高温下其放电容量达到525.6 mAh·g^-1.     

B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应中的溶剂效应

 采用不同极性的溶剂作为环己酮肟的溶剂,考察了溶剂极性对B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应性能的影响. 结果表明,除乙醇外,随着溶剂极性的增大,己内酰胺的收率逐渐提高. 在所考察的溶剂范围内,当采用极性最强的乙腈为溶剂时,B2O3/TiO2-ZrO2的催化性能最佳,连续反应9 h,环己酮肟的转化率为100%,己内酰胺的选择性高达98.6%. 极性较强的溶剂可显著改善B2O3/TiO2-ZrO2催化性能的原因主要是其有利于反应所生成的己内酰胺从催化剂表面快速脱附,从而可抑制己内酰胺进一步发生聚合及分解等副反应.     

环己酮肟在B2O3/Al2O3-TiO2催化剂上的气相Beckmann重排反应

制备了B2O3/Al2O3-TiO2复合载体催化剂,并考察了其对环己酮肟气相Beckmann重排制己内酰胺反应的催化性能. 结果表明,载体中TiO2的含量、B2O3的负载量、载体的预处理温度及催化剂的焙烧温度等均对催化剂的性能产生明显的影响. 当载体中TiO2含量为60%,B2O3负载量为20%,催化剂经350 ℃焙烧时,环己酮肟的气相Beckmann重排反应的转化率和选择性很高. 用BET,NH3-TPD,XRD和IR等方法对催化剂的织构、表面酸性和晶相等进行了表征,并与催化剂的活性进行了关联,表明催化剂表面中等强度的酸中心浓度与催化剂的选择性具有对应关系.     

氮化硼纤维先驱体的制备与表征

以三氯环硼氮烷为原料, 将其与正丙胺/异丙胺进行共取代反应, 制得了不同结构的取代单体, 再经热聚合反应获得了相应的聚硼氮烷先驱体. 通过分析不同正丙胺/异丙胺配比制得的聚合产物的组成与结构, 探讨了不同单体的胺基取代基对先驱体的聚合反应性及对产物结构的影响. 结果表明, 当正丙胺/异丙胺摩尔比为2∶1, 聚合温度为150 ℃, 反应时间为10 h时, 合成产物具有近似线性分子结构, 熔点为90 ℃, 具有良好的成丝性, 可获得平均直径10~20 μm, 组成为BC_1.27N_1.52H_x的先驱体纤维, 先驱体纤维再经不熔化处理及1200 ℃氨气高温煅烧等工艺可获得近化学计量比的氮化硼纤维.     

氮化硼载体对 Ru-Ba/BN 氨合成催化剂性能的影响

 研究了不同方法合成的氮化硼 (BN) 的性质及其负载的 Ru-Ba 催化剂对氨合成的催化性能. 采用 X 射线粉末衍射、N2 吸附-脱附、扫描电镜和傅里叶变换红外光谱等手段对所合成的 BN 样品进行了表征. 结果表明, 采用程序升温氮化和程序升温还原法均能在低于 900 oC 的条件下合成出较纯的六方相 BN, 其比表面积分别达到 103 和 138 m2/g. 其中前者负载 Ru-Ba 的催化剂活性更高, 在 475 oC, 10 MPa 和 10 000 h–1 的条件下出口氨浓度达 7.3%, 且在 550 oC 热处理 30 h 后, 活性基本保持不变.