Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Nat Chem. 2012 Nov;4(11):934-40. doi: 10.1038/nchem.1476. Epub 2012 Oct 21.
Industrially, the artificial fixation of atmospheric nitrogen to ammonia is carried out using the Haber-Bosch process, but this process requires high temperatures and pressures, and consumes more than 1% of the world's power production. Therefore the search is on for a more environmentally benign process that occurs under milder conditions. Here, we report that a Ru-loaded electride Ca(24)Al(28)O(64)(e(-))(4) (Ru/C12A7:e(-)), which has high electron-donating power and chemical stability, works as an efficient catalyst for ammonia synthesis. Highly efficient ammonia synthesis is achieved with a catalytic activity that is an order of magnitude greater than those of other previously reported Ru-loaded catalysts and with almost half the reaction activation energy. Kinetic analysis with infrared spectroscopy reveals that C12A7:e(-) markedly enhances N(2) dissociation on Ru by the back donation of electrons and that the poisoning of ruthenium surfaces by hydrogen adatoms can be suppressed effectively because of the ability of C12A7:e(-) to store hydrogen reversibly.
在工业上,通过哈伯-博世(Haber-Bosch)工艺实现大气氮气的人工固定为氨,但是这个过程需要高温高压,并且消耗了超过 1%的世界电力产量。因此,人们正在寻找一种在更温和条件下发生的、环境更友好的工艺。在这里,我们报告了一种负载钌的电子导体 Ca(24)Al(28)O(64)(e(-))(4)(Ru/C12A7:e(-)),它具有高的电子给予能力和化学稳定性,可用作氨合成的高效催化剂。与其他之前报道的负载 Ru 催化剂相比,该催化剂具有大一个数量级的催化活性,并且反应活化能几乎降低一半,从而实现了高效的氨合成。通过红外光谱的动力学分析揭示,C12A7:e(-)通过电子的反向给予显著增强了 Ru 上的 N2 离解,并且由于 C12A7:e(-)能够可逆地储存氢气,Ru 表面的氢原子的毒化可以被有效地抑制。