Gi Hiroyuki, Shinzato Keita, Balgis Ratna, Ogi Takashi, Sadakane Masahiro, Wang Yongming, Isobe Shigehito, Miyaoka Hiroki, Ichikawa Takayuki
Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527, Japan.
Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527, Japan.
ACS Omega. 2020 Aug 21;5(34):21906-21912. doi: 10.1021/acsomega.0c03101. eCollection 2020 Sep 1.
Magnesium is a promising hydrogen storage material but requires an efficient catalyst to enhance the sluggish kinetics of its hydrogen desorption/absorption reactions. Niobium catalysts have been shown to accomplish this, but the effective factors for catalysis on hydrogen desorption/absorption of Mg are not well understood. In order to investigate these aspects, various types of Nb oxides were synthesized and mixed with Mg, and their catalytic properties were investigated. The spray pyrolysis synthesis of Nb oxides at different temperatures produced homogeneous spherical particles with different degrees of crystallinity, while Nb oxide particles synthesized by simple calcination of ammonium niobium oxalate were nonuniform. These Nb oxides show significant catalytic activities for the hydrogen desorption/absorption of Mg, with amorphous oxides being more effective catalyst precursors than crystalline precursors. Metastable, amorphous Nb oxide is more easily converted to the reduced state, which is the catalytically active state for the reactions. In addition, Nb in the deactivated sample is in the oxidized state compared with the initially activated sample, and the catalytically active (reduced) state is recovered by reactions with hydrogen. Based on these findings, it is concluded that the chemical state of Nb is an important factor in catalyzing the desorption/absorption of hydrogen by Mg, and the catalytically active state can be preserved without further treatments.
镁是一种很有前景的储氢材料,但需要一种高效催化剂来加速其氢解吸/吸收反应缓慢的动力学过程。已证明铌催化剂能实现这一点,但对于镁氢解吸/吸收催化作用的有效因素尚未完全了解。为了研究这些方面,合成了各种类型的铌氧化物并与镁混合,并对其催化性能进行了研究。在不同温度下通过喷雾热解合成的铌氧化物产生了具有不同结晶度的均匀球形颗粒,而通过草酸铌铵简单煅烧合成的铌氧化物颗粒则不均匀。这些铌氧化物对镁的氢解吸/吸收表现出显著的催化活性,非晶态氧化物比晶态前体更有效地作为催化剂前体。亚稳态的非晶态铌氧化物更容易转化为还原态,这是反应的催化活性状态。此外,与初始活化样品相比,失活样品中的铌处于氧化态,通过与氢反应可恢复催化活性(还原)状态。基于这些发现,得出结论:铌的化学状态是催化镁氢解吸/吸收的一个重要因素,并且催化活性状态无需进一步处理即可保留。