Valentoni Antonio, Mulas Gabriele, Enzo Stefano, Garroni Sebastiano
Department of Chemistry and Pharmacy, Università degli Studi di Sassari e INSTM, Via Vienna 2, I-07100 Sassari, Italy.
Phys Chem Chem Phys. 2018 Feb 7;20(6):4100-4108. doi: 10.1039/c7cp07157d.
The present work concerns the catalytic effect of VNbO, a ternary oxide prepared via a solid-state route, on the sorption performance of MgH. Three doped systems, namely 5, 10 and 15 wt% VNbO-MgH have been prepared by ball milling and thoroughly characterized. Hydrogen sorption, evaluated by temperature programmed desorption experiments, revealed a significant reduction of the desorption temperature from 330 °C for the un-doped sample (prepared and tested for comparison) to 235 °C for the VNbO-doped sample. Furthermore, more than 5 wt% of hydrogen can be absorbed in 5 minutes at 160 °C under 20 bar of hydrogen, which is remarkable compared to the 0.7 wt% achieved for the un-doped system. The sample doped with 15 wt% of additive, showed good reversibility: over 5 wt% of hydrogen with negligible degradation even after 70 consecutive cycles at 275 °C and 50 cycles at 300 °C. The kinetics analysis carried out by Kissinger's method exhibited a considerable reduction of the activation energy for the desorption process. Finally, pressure-composition-isotherm experiments conducted at three different temperatures allowed estimating the thermodynamic stability of the system and shed light on the additive role of VNbO.
本工作涉及通过固态路线制备的三元氧化物VNbO对MgH吸附性能的催化作用。通过球磨制备了三种掺杂体系,即5 wt%、10 wt%和15 wt%的VNbO-MgH,并对其进行了全面表征。通过程序升温脱附实验评估氢吸附情况,结果表明,脱附温度从未掺杂样品(为作比较而制备和测试)的330℃显著降低至VNbO掺杂样品的235℃。此外,在160℃、20 bar氢气压力下,5分钟内可吸收超过5 wt%的氢,与未掺杂体系实现的0.7 wt%相比,这一结果非常显著。掺杂15 wt%添加剂的样品显示出良好的可逆性:即使在275℃连续循环70次和300℃循环50次后,仍有超过5 wt%的氢,且降解可忽略不计。用基辛格方法进行的动力学分析表明,脱附过程的活化能显著降低。最后,在三个不同温度下进行的压力-组成等温线实验能够估算该体系的热力学稳定性,并阐明VNbO的添加剂作用。