Laboratoire Catalyse et Spectrochimie, ENSICAEN, Université de Caen, CNRS, 6, Boulevard Maréchal Juin, 14050 Caen, France.
Chemistry. 2012 Sep 17;18(38):11959-67. doi: 10.1002/chem.201201006. Epub 2012 Aug 13.
A reducible MIL-100(Fe) metal-organic framework (MOF) was investigated for the separation of a propane/propene mixture. An operando methodology was applied (for the first time in the case of a MOF) in order to shed light on the separation mechanism. Breakthrough curves were obtained as in traditional separation column experiments, but monitoring the material surface online, thus providing evidences on the adsorption sites. The qualitative and quantitative analyses of Fe(II) and, to some extent, Fe(III) sites were possible, upon different activation protocols. Moreover, it was possible to identify the nature and the role of the active sites in the separation process by selective poisoning of one family of sites: it was clearly evidenced that the unsaturated Fe(II) sites are mainly responsible for the separation effect of the propane/propene mixture, thanks to their affinity for the unsaturated bonds, such as the C=C entities in propene. The activity of the highly concentrated Fe(III) sites was also highlighted.
一种可还原的 MIL-100(Fe) 金属有机骨架（MOF）被用于研究丙烷/丙烯混合物的分离。采用了一种原位方法（在 MOF 的情况下首次应用），以便深入了解分离机制。获得了与传统分离柱实验相同的穿透曲线，但在线监测材料表面，从而提供了吸附位的证据。通过不同的激活方案，可以对 Fe(II)和在一定程度上 Fe(III)位进行定性和定量分析。此外，通过选择性毒化一个配体家族的位，可以识别分离过程中活性位的性质和作用：显然，不饱和 Fe(II)位主要负责丙烷/丙烯混合物的分离效果，这要归功于它们对不饱和键的亲和力，例如丙烯中的 C=C 基团。高浓度 Fe(III)位的活性也得到了强调。
