H_4PMo_(11)VO_(40)催化氧化2-甲基萘制备甲萘醌

以磷钼钒杂多酸H4PMo11V1O40为催化剂、乙酸为溶剂,用双氧水氧化2-甲基萘制备2-甲基萘醌.实验表明:H4PMo11V1O40具有一定的催化活性.通过正交试验和单因素试验考察了催化剂用量、乙酸用量、双氧水用量、反应时间、反应温度等对收率的影响,获得较佳的合成条件:杂多酸∶2-MN(质量比)=7%,乙酸∶2-MN(质量比)=10.5∶1,双氧水∶2-甲基萘(摩尔比)=4.2∶1,较适宜的温度为40~50℃,反应时间为30 min.     

L-抗坏血酸紫外分光光度法检测微量过氧化氢

建立了L-抗坏血酸（L—Aseorbieacid）紫外分光光度法测定微量过氧化氢的新方法．在pH=5．7的磷酸缓冲溶液介质中,选择273nm作为测定波长,过氧化氢的摩尔浓度在0～0．1mmol／L范围内服从比尔定律．回归方程为：y=0．0049＋4．44612x（mmol／L）,检出限为0．401μmol／L．该法用于溶液中、生物组织等样品中微量过氧化氢浓度的测定,快速简便．     

化学氧化法精制11-氰基十一酸

以11-氰基十一酸(11-CUA)的纯度和收率为目标函数,采用三种不同的氧化剂精制粗品11-氰基十一酸,通过对比实验及对氧化产物的红外光谱解析与熔点测定,确定了双氧水是合适的氧化剂.再利用正交试验对双氧水精制11-氰基十一酸的工艺条件进行研究,得到优化实验条件:在双氧水质量分数为15%、温度为20℃、pH值为2.0、反应时间30 min的条件下精制粗品11-CUA,产品纯度达99.86%,收率93.62%.     

C6H5NH-H□X分子间氢键的理论研究

在B3LYP／6-311＋＋G（3df,2p）理论水平上,对C6H5NH-H□X（X=H2O,HCOH,CH3COCH3,NH3,CH2NH和HCN）氢键体系进行几何结构优化与振动频率计算,在所得稳定构型的基础上进行自然键轨道分析和热力学性质研究．结果表明,C6H5NH-H□X体系存在较弱的N—H□O与N—H□N氢键,氢键的形成使H—N伸缩振动频率明显红移．在298．15K和标准状态下,C6H5NH-H□X体系分子在气相的形成过程是一个放热、熵减的非自发过程．     

单壁碳纳米管储氢分子动力学模拟研究

选用C(10×10)扶手椅型单壁纳米管,采用分子动力学方法模拟研究了在温度100K,初始入射动能在10,30,50,80,100eV几种情况下氢原子在单壁碳纳米管中的运动,并分析了单壁碳纳米管储氢情况,得到初始能量为80eV时储氢效果较好.     

Hydrogen generation from decomposition of hydrous hydrazine over Ni-Ir/CeO2 catalyst

The synthesis of highly active and selective catalysts is the central issue in the development of hydrous hydrazine(N_2H_4·H_2O) as a viable hydrogen carrier. Herein, we report the synthesis of bimetallic Ni-Ir nanocatalyts supported on CeO_2 using a one-pot coprecipitation method. A combination of XRD, HRTEM and XPS analyses indicate that the Ni-Ir/CeO_2 catalyst is composed of tiny Ni-Ir alloy nanoparticles with an average size of around 4 nm and crystalline CeO_2 matrix. The Ni-Ir/CeO_2 catalyst exhibits high catalytic activity and excellent selectivity towards hydrogen generation from N_2H_4·H_2O at mild temperatures. Furthermore, in contrast to previously reported Ni-Pt catalysts, the Ni-Ir/CeO_2 catalyst shows an alleviated requirement on alkali promoter to achieve its optimal catalytic performance.     

Synergic catalytic effect of Ti hydride and Nb nanoparticles for improving hydrogenation and dehydrogenation kinetics of Mg-based nanocomposite

The Mg-9.3 wt% (TiH1.971-TiH)?0.7 wt% Nb nanocomposite has been synthesized by hydrogen plasma-metal reaction (HPMR) approach to enhance the hydrogen sorption kinetics of Mg at moderate temperatures by providing nanosizing effect of increasing H “diffusion channels” and adding transition metallic catalysts. The Mg nanoparticles (NPs) were in hexagonal shape range from 50 to 350 nm and the average size of the NPs was 177 nm. The small spherical TiH1.971, TiH and Nb NPs of about 25 nm uniformly decorated on the surface of the big Mg NPs. The Mg-TiH1.971-TiH-Nb nanocomposite could quickly absorb 5.6 wt% H2 within 5 min at 573 K and 4.5 wt% H2 within 5 min at 523 K, whereas the pure Mg prepared by HPMR could only absorb 4 and 1.5 wt% H2 at the same temperatures. TiH1.971, TiH and Nb NPs transformed into TiH2 and NbH during hydrogenation and recovered after dehydrogenation process. The apparent activation energies of the nanocomposite for hydrogenation and dehydrogenation were 45.0 and 50.7 kJ mol?1, which are much smaller than those of pure Mg NPs, 123.8 and 127.7 kJ mol?1. The improved sorption kinetics of the Mg-based nanocomposite at moderate temperatures and the small activation energy can be interpreted by the nanostructure of Mg and the synergic catalytic effects of Ti hydrides and Nb NPs.     

EQCM技术对电化学振荡机理的探索

利用石英晶体微天平技术对H2O2在硫酸,高氯酸和盐酸等酸性介质中铂电极上还原反应产生的电化学振荡行为进行了较为系统的研究,得到了对应于H2O2还原过程中两类不同电流振汇的频率响应曲线,讨论了可能的电化学振荡机制。     

过氧化氢分子的键能和成键特性的CNDO/2研究

H2O2分子中的O—H键比H2O的略长．而键振动频率v^-和计算的键能EAB值表明．H2O2分子中的O—H键则略强于H2O的。本用CNDO／2方法对其键能进行了计算．并对这一“反常”现象进行了解释。     

锈蚀钢筋混凝土梁抗冲击荷载数值模拟研究

为研究冲击作用下锈蚀钢筋混凝土梁的力学性能与破坏模态,通过混凝土梁冲击试验,校核了有限元软件ANSYS/LS-DYNA建立的钢筋混凝土梁结构精细化有限元模型的冲击力时程曲线、跨中位移时程曲线和破坏模态的准确性。在已验证有限元模型的基础上,研究钢筋锈蚀率对混凝土梁抗冲击性能的影响。有限元分析表明：混凝土构件在冲击作用下导致的混凝土剥落程度随钢筋锈蚀率的增加而增加。各冲击高度下的锈蚀钢筋混凝土梁均表现出弯曲破坏特征。钢筋锈蚀对钢筋混凝土构件的抗冲击性能具有一定的影响,在相同落锤冲击高度下,冲击力峰值随钢筋锈蚀率的增大逐渐减小,跨中位移随钢筋锈蚀率的增大而增大。当冲击高度为3.0 m时,锈蚀率为30.0%时的冲击力峰值降低到未锈蚀时的17.9%,跨中位移为增加到未锈蚀时的33.3%。