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首页> 外文会议>TMS(The Minerals, Metals amp; Materials Society) Annual Meeting and Symposium on Advanced Materials for Energy Conversion II; 20040314-20040318; Charlotte,NC; US >Dehydrogenation Process of Titanium and Zirconium Doped Alanates
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Dehydrogenation Process of Titanium and Zirconium Doped Alanates

机译：钛锆掺杂丙酸酯的脱氢工艺

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Dehydrogenation process of Ti and Zr doped alanates was studied by means of the thermal gravimetry-differential thermal analysis (TG-DTA) and isothermal dehydrogenation kinetics measurement. With using transmission electron microscope (TEM) equipped with an electron energy loss spectrometer (EELS), we observed the distribution of Ti element on a particle of the Ti doped material. The kinetic measurement showed that: (ⅰ) Dehydrogenation of Na_3AlH_6 proceeds much slower than that of NaAlH_4, when the former is observed as a second step of the two step consecutive dehydrogenation of Ti doped NaAlH_4. (ⅱ) But if Na_3AlH_6 is doped directly with Ti, the dehydrogenation rate matches that of NaAlH_4. (ⅲ) The activation enthalpies of both Ti doped NaAlH_4 and Na_3AlH_6 are 100 kJ·mol~(-1), and those of both Zr doped NaAlH_4 and Na_3AlH_6 are 135 kJ·mol~(-1). These findings imply that the rate determinig step is not related to the cleavage of Al-H bonding, which must be sensitive to whether the species involved is [AlH_4]~- or [AlH_6]~(3-), but to a long range phenomenon, such as the diffusion of the atom in the particle. The TEM-EELS observation showed that the Ti element was distributed on the surface of the particle of doped material.
机译：通过热重分析-差示热分析（TG-DTA）和等温脱氢动力学测量，研究了Ti和Zr掺杂铝酸盐的脱氢过程。使用配备有电子能量损失谱仪（EELS）的透射电子显微镜（TEM），我们观察到了Ti元素在Ti掺杂材料的颗粒上的分布。动力学测量显示：（3）当观察到前者是掺钛的NaAlH_4的两步连续脱氢的第二步时，Na_3AlH_6的脱氢比NaAlH_4的脱氢慢得多。 （ⅱ）但是，如果将Na_3AlH_6直接掺杂Ti，则脱氢率与NaAlH_4相同。 （ⅲ）Ti掺杂的NaAlH_4和Na_3AlH_6的活化焓均为100 kJ·mol〜（-1），Zr掺杂的NaAlH_4和Na_3AlH_6的活化焓均为135 kJ·mol〜（-1）。这些发现表明，速率确定步骤与Al-H键的断裂无关，Al-H键的断裂必须对所涉及的物种是[AlH_4]〜-或[AlH_6]〜（3-）敏感，但范围很广。现象，例如原子在粒子中的扩散。 TEM-EELS观察表明，Ti元素分布在掺杂材料的颗粒表面上。

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