Catalytic effect and reaction mechanism of Ti doped in NaAlH4: A review

Catalytic effect and hydrogen reaction mechanism of Ti doped in NaAlH4 were elaborated in this paper, and currant viewpoints about Ti active species in hydrogen reaction were discussed, In a further step, the possibility and practicality of the hydrogen reaction mechanism of Ti-doped NaAlH4 were elucidated, They could be summarized as follows： while the current theory about the hydrogen reaction mechanism of Ti-doped NaAlH4 should be further improved and modified, the research on Ti-doped NaAlH4 would be a recommendable pattern for the catalyst research in other metal complex hydrides,     

Enhanced hydrogen storage of alanates: Recent progress and future perspectives

The global energy crisis and environmental pollution have caused great concern. Hydrogen is a renewable and environmentally friendly source of energy and has potential to be a major alternative energy carrier in the future.Due to its high capacity and relatively low cost of raw materials, alanate has been considered as one of the most promising candidates for hydrogen storage. Among them, LiAlH₄ and NaAlH₄, as two representative metal alanates, have attracted extensive atte...     

Wox-Ti薄膜的电致变色性能

为了提高WOx薄膜的电致变色性能,笔者采用磁控反应溅射工艺,以纯钨和纯钛为靶材在ITO玻璃上制备Ti掺杂WOx电致变色薄膜,用薄膜的透射光谱和XRD衍射方法对掺杂后薄膜的电致变色性能和结构进行了分析,研究了Ti掺杂对WOx薄膜电致变色性能和微观结构的影响机理.实验表明:Ti掺杂不会降低WOx薄膜的致色效果,还能显著提高薄膜的循环寿命,缩短响应时间,提高记忆存储能力,XRD分析表明,掺杂Ti之后的WOx薄膜仍为非晶态,且非晶态有增强的趋势.     

纯Ti(BH_4)_3·5NH_3的制备及储氢性能

氨合硼氢化钛是一类放氢温度适宜的高容量储氢材料,但已报道的通过球磨法制备的氨合硼氢化钛通常含有质量分数42%以上的LiCl杂质,降低了体系总含氢量的同时也为氨合硼氢化钛本征放氢性能的表征带来了困难.因此,纯氨合硼氢化钛的制备和性能表征十分必要.本文以钛酸四异丙酯、乙硼烷、四氢呋喃和NH_3为初始原料,通过先制备前驱体Ti(BH_4)_3·2THF,然后再氨化的二步反应首次成功合成纯Ti(BH_4)_3·5NH_3,并对前驱体和氨合硼氢化钛的组成、结构和放氢性能进行系统地研究.结果表明,前驱体Ti(BH_4)_3·2THF属于斜方晶系,Pbcn空间群,且在室温下能稳定存在,是制备氨合硼氢化钛的良好前驱体;纯Ti(BH_4)_3·5NH_3具有良好的放氢性能,于75℃开始放氢,至200℃释放质量分数约10%的氢气.     

Electronic structure of edge dislocation of core-doped Ti in Fe

The electronic structure of an edge dislocation doped Ti lying in the (001) plane with Burgers Vector along [100] direction in body-centered cubic iron is investigated using the first principles discrete variational method (DVM) based on the density-functional theory. The binding energy, impurity formation energy, interatomic energy, Mulliken orbital populations and charge density difference are presented in this paper. By calculating the binding energy of the clean dislocation system and the Ti-doped system, it is found that the binding energy of Ti-doped dislocation system is lower than that of the clean dislocation system, which implies that the Ti-doped dislocation system is more stable than the clean dislocation system. The calculated result of the impurity formation energy predicts the trapping effect of dislocation core for Ti, which shows that Ti atom prefers to occupy the place at the dislocation core. The calculated results of the interatomic energy and the difference charge density of dislocation doped Ti system indicate that the stronger bonding formed between the Ti impurity and its neighbor Fe atoms will affect the mechanical property of edge dislocation. Considering the influence of Ti on the electronic structure and the energies, we can predict that the trace Ti in transition metal Fe with dislocation defect can give a significant contribution to the solid solution hardening effects and will influence the mechanical property of materials.     

离子束修饰提高钛阴极析氢活性

研究了双重离子注入Ｗ＾＋／Ｎｉ＾＋,Ｗ＾＋／Ｍｏ＾＋及溅射Ｆｅ后再单离子注入Ｃｏ＾＋或Ｗ＾＋等离子束修饰的钛电极在１ＮＨ２ＳＯ４中的析氢电催化性能,结果表明：与纯钛电极相比,离子束修饰电极的催化析氢活性得到显著改善,其中,注Ｗ＾＋／Ｎｉ＾＋电极的析氢过电位降低３００ｍＶ,用ＸＰＳ和ＡＥＳ能谱分析了离子束修饰电极的表面元素及相结构,讨论了修饰电极催化所氢机理。     

Microstructure characterization and hydrogen storage properties study of Mg2Ni0.92M0.08 (M = Ti, V, Fe or Si) alloys

In the present study Mg_2Ni-type compounds alloyed independently with Ti,V,Fe and Si were successfully prepared by wet-milling followed by sintering.Although these alloyed Mg_2Ni compounds exhibited a similar hydrogen storage mechanism as that of pure Mg_2Ni,the dissolution of Ti,V or Fe into the Mg_2NiH_4lattice had a considerable catalytic effect on hydrogen desorption from additional MgH_2.The further structure investigations clearly indicated that the substitution of Ti for Ni could suppress the formation of the micro-twined low-temperature phase(LT2)and promote the formation of the high-temperature phase(HT),thus resulting in remarkably improved hydrogen desorption kinetics for the Mg_2Ni_(0.92)Ti_(0.08)–H system.     

电解海水阴极析氢非贵金属电催化剂研究进展

氢能具有高能量密度、绿色可持续的优点,是人类社会的理想能源。电解海水制氢是未来氢能产业的战略方向,其中阴极析氢催化剂的活性和稳定性对电解海水制氢的发展至关重要。贵金属铂虽具备优异的析氢催化性能,但价格昂贵、资源有限,限制了其大规模应用。因此,对非贵金属催化剂的研究备受关注。从析氢反应原理入手,介绍了过电位、塔菲尔斜率、法拉第效率、比活性和质量活性等评价催化性能的几个重要参数,综述分析了多种非贵金属催化剂作为电解海水制氢阴极催化剂的研究现状,指出了目前电解海水制氢面临的问题,认为未来非贵金属催化剂规模化电解海水阴极析氢研究应从以下几方面开展：1）设计高活性和稳定性的非贵金属催化剂;2）优化非贵金属催化剂的制备工艺;3）利用先进测试表征手段辅助构建反应模型;4）深化理论计算机理方面的研究。     

Ti对LiAlH4储氢性能的影响

为了降低LiAlH4的吸放氢温度及提高其吸放氢速度,采用基于密度泛函理论(DFT)的平面波赝势(PW-PP)方法,计算了Ti掺杂在LiAlH4中取代不同位置的Li、Al前后的电子结构及相关热力学性质。结构优化之后,热力学稳定性较好的构型有4种:Li3Al4H16Ti、Li4Al3H16Ti、Li3Al4H17Ti、Li4Al3H17Ti,其对应的缺陷形成能分别为1.31、0.60、1.21、1.27 eV。掺杂前后LiAlH4的电子态密度并无明显变化。在LiAlH4化学势变化曲线图中,TiAl3的化学势变化曲线与反应物LiAlH4、Li3AlH6等的并没有相交。上述结果表明,单质的Ti对LiAlH4的分解并没有起到实质的催化作用。     

Ru基氧化物涂层钛阴极的电功能及析氢效应

通过强化寿命实验(ALTT)、扫描电镜(SEM)表面分析、X射线衍射、循环伏安及极化曲线等测试,研究含钌氧化物涂层钛阴极在1mol LH2SO4溶液中析氢过程的催化活性、寿命及失效机制.结果表明:含Ru氧化物涂层阴极在析氢过程的特性吸附,表现出比钛阴极低的析氢过电位、高的强化寿命和稳定的电功能,最终以剥落失效.     

Environmental embrittlement of intermetallics

The effect of alloying elements on the environmental embrittlement of L12 type intermetallics is sum marized. The results show that the ductilizing effect of boron doping in Ni3A1 is mainly to suppress the moisture-induced environmental embrittlement. The mechanism of this suppression effect is proved to lie in the fact that it severely reduces the hydrogen diffusivity along the grain boundaries. However, the boron doping in Co3Ti alloys does not have the same effect of suppressing the environmental embrittlement. The different behavior of boron doping in Ni3A1 and Co3Ti may be attributed to its different segregation behavior on the grain boundaries. Boron in Co3Ti does not segregate on the grain boundaries and cannot effectively reduce the hydrogen diffusivity along the grain boundaries. The moisture-induced envi ronmental embrittlement of Co3Ti alloy can be completely suppressed by the addition of Fe. As proved by Auger, this suppression effect is due to its obvious reduction of the surface kinetic reaction with water vapor.     

自蔓延高温合成钒基固溶体贮氢合金的理论研究

提出采用自蔓延高温合成法制备钒基固溶体贮氢合金的新工艺.计算知NH4VO3-TiO2-Cr2O3-Ni-Al反应体系的绝热温度(Tad)为1 889.27 K,单位质量反应热为-2.67 kJ/g;对NH4VO3-TiO2-Cr2O3-Ni-Al反应体系的相关反应进行了热力学分析,表明体系生成V+Ti+Cr+Al2O3的趋势最大,生成物最稳定.确定了采用自蔓延模式的可行性.     

TiO2百微米空心球的可控制备及机理

通过水热法成功制备了直径为100³00μm的TiO2百微米球;采用SEM、TEM表征的结果显示了得到的百微米球是由大量TiO2纳米线自组装成的空心球;对TiCl4的浓度、反应温度、反应时间对产品的影响进行了研究,并讨论了TiO2百微米球的生长机理.     

Effect of heat treatment on hydrogen storage properties and thermal stability of V68Ti20Cr12 alloy

Effect of heat treatment on the crystal structure, microstructure, hydrogen storage properties and thermal stability of V68Ti20Cr12 alloy prepared by arc-melting was studied in this work. It was found that both the as-cast and annealed (973 K/72 h) V68Ti20Cr12 alloys consisted of a single body-centered cubic (bcc) phase. After heat treatment, the hydrogen absorption/desorption kinetic characteristics of the as-cast alloy was improved greatly due to the homogeneous composition and perfect structure. The mechanism of hydrogen absorption/desorption process in the as-cast and annealed alloys was further investigated according to the Johnson-Mehl-Avrami (JMA) equation. The hydrogen absorption process of the as-cast and annealed alloys would be controlled by the one-dimensional diffusion process, while the hydrogen desorption process in the as-cast and annealed alloys was dominated by the geometrical contraction model. The pressure-composition-temperature (PCT) measurements show that the plateau pressure of the annealed alloy becomes comparatively flat. Furthermore, the activation energies of the dehydrogenation in the as-cast and annealed alloys were calculated using the Kissinger method, indicating that heat treatment is a very beneficial way to improve hydrogen absorption/desorption kinetics of the alloy.     

高温注氢对钒合金微观结构的影响

研究了500℃高温条件下注氢对V-4Cr、V-4Ti和V-4Cr-4Ti三种合金微观结构的影响。在注氢实验之前,V-4Cr合金的基体清晰干净,而V-4Ti和V-4Cr-4Ti两种合金的基体中则出现很多相互平行和垂直的针状析出相,且大部分析出相周围都存在着位错。在500℃注氢实验之后,V-4Cr合金基体中出现大量的分布不均的黑色点状缺陷和缺陷簇,而V-4Ti和V-4Cr-4Ti两种合金的基体中除产生点状缺陷外,还出现高密度的气泡,且V-4Cr-4Ti合金中气泡的平均尺寸要稍小一些。另外,V-4Ti和V-4Cr-4Ti合金基体中原有的析出相在注氢实验之后都发生不同程度的溶解。在观察V-4Cr-4Ti合金基体中气泡分布规律时发现,在距离晶界25 nm的范围内几乎看不到气泡的存在,由此推断晶界的存在可以抑制氢气泡等辐照缺陷的产生。     

非铁电性巨介电材料CaCu3Ti4O12的研究进展

目的综述介电材料CaCu3Ti4O12(CCTO)研究的新进展,提出本研究领域需要进一步深入的方面,并在此基础上分析其发展前景。方法在介绍CCTO相结构的基础上,对其巨介电机制模型、制备方法、掺杂改性及其复合材料的研究进展进行总结。结果根据CCTO巨介电机制模型,设计新的巨介电材料或者复合材料,进一步降低其介电损耗,开发该类巨介电材料的应用新领域。结论 CCTO陶瓷具有巨介电常数及优异的温度稳定性,进一步降低其介电损耗将有很好的应用前景。     

机械合金化法制备Cu-Ti-Zr基非晶合金

采用机械合金化法成功制备Cu40Ti60-xZr(x=0,10,30,50)非晶合金.研究Cu-Ti-Zr合金粉末由晶态向非晶态转变过程中的组织结构变化,探讨非晶合金的形成机制,以及非晶合金的热稳定性和晶化产物.结果表明,非晶合金直接从初始元素得到,在反应过程中没有金属间化合物出现,非晶化过程可以由间隙扩散模型来解释.Cu40TixZry非晶粉末的DSC分析表明,随着Ti含量的降低和Zr含量的升高,非晶粉末的晶化温度Tx逐渐升高,对非晶粉末在相应的Tx温度附近退火15min后发现,Cu40Ti30Zr30合金没有析出相,Cu40Ti1Zr50析出了Zr2Cu,Cu4Ti和少量的一些未知相.     

La2Mo2O9的离子掺杂行为研究

以柠檬酸为络合剂,采用溶胶-凝胶法合成了La2Mo2O9以及La2Mo2-xMxO9(M=Fe、Mn、Ti、Co、Ni、W)掺杂的样品.应用X射线衍射(XRD)、差示扫描量热(DSC)等方法考察了离子掺杂的成相情况以及离子搀杂对La2Mo2O9结构的稳定化作用;运用双探针法测试了样品的电导率随温度的变化情况.研究结果表明Fe、Mn、Ti、Co、Ni等离子对Mo6 的取代掺杂量较少.纯La2Mo2O9在580℃左右存在相变,但Fe、Ti掺杂样品没有出现相变过程的吸热峰.W6 离子可取代部分Mo6 而进入La2Mo2O9晶格,但对抑制其相变没有作用.     

高介电常数CaCu_3Ti_4O_(12)陶瓷材料的研究现状

CaCu3Ti4O12(CCTO)陶瓷材料因具有反常的高介电常数以及优异的温度稳定性而显示出广泛的应用前景.介绍了CCTO陶瓷材料的晶体结构、制备方法、介电性能和微观介电机制,综述了CCTO陶瓷材料的介电性能改性方面的研究现状.     

锂离子电池正极材料LiFePO4的制备及电化学性能研究

∶采用高温固相法合成LiFePO4锂离子电池正极材料,为提高LiFePO4材料的电化学性能,对其进行Ti4 掺杂改性.用XRD、SEM等测试手段对材料进行表征,并对以Li1-xTixFePO4(x=0,0.01,0.03,0.05)为正极的电池进行电化学性能测试.研究表明,掺杂过程中,掺杂离子能与LiFePO4形成晶格完整、有序的单相固溶体;少量的掺杂离子还可以提高材料的电导率和电化学性能,特别是大电流放电性能,其中Li0.97Ti0.03FePO4性能最优,以0.2C5放电,首次放电质量比容量为132.0 mA.h/g,50次循环后仍保持为131.5 mA.h/g.