Schröder Felicitas, Esken Daniel, Cokoja Mirza, van den Berg Maurits W E, Lebedev Oleg I, Van Tendeloo Gustaaf, Walaszek Bernadeta, Buntkowsky Gerd, Limbach Hans-Heinrich, Chaudret Bruno, Fischer Roland A
Lehrstuhl für Anorganische Chemie II-Organometallics & Materials, Ruhr-Universität, Universitätsstrasse 150, D-44780 Bochum, Germany.
J Am Chem Soc. 2008 May 14;130(19):6119-30. doi: 10.1021/ja078231u. Epub 2008 Apr 11.
The gas-phase loading of [Zn4O(bdc)3] (MOF-5; bdc = 1,4-benzenedicarboxylate) with the volatile compound [Ru(cod)(cot)] (cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene) was followed by solid-state (13)C magic angle spinning (MAS) NMR spectroscopy. Subsequent hydrogenolysis of the adsorbed complex inside the porous structure of MOF-5 at 3 bar and 150 degrees C was performed, yielding ruthenium nanoparticles in a typical size range of 1.5-1.7 nm, embedded in the intact MOF-5 matrix, as confirmed by transmission electron microscopy (TEM), selected area electron diffraction (SAED), powder X-ray diffraction (PXRD), and X-ray absorption spectroscopy (XAS). The adsorption of CO molecules on the obtained Ru@MOF-5 nanocomposite was followed by IR spectroscopy. Solid-state (2)H NMR measurements indicated that MOF-5 was a stabilizing support with only weak interactions with the embedded particles, as deduced from the surprisingly high mobility of the surface Ru-D species in comparison to surfactant-stabilized colloidal Ru nanoparticles of similar sizes. Surprisingly, hydrogenolysis of the [Ru(cod)(cot)]3.5@MOF-5 inclusion compound at the milder condition of 25 degrees C does not lead to the quantitative formation of Ru nanoparticles. Instead, formation of a ruthenium-cyclooctadiene complex with the arene moiety of the bdc linkers of the framework takes place, as revealed by (13)C MAS NMR, PXRD, and TEM.
通过固态（13）C魔角旋转（MAS）核磁共振光谱法跟踪了挥发性化合物[Ru（cod）（cot）]（cod = 1,5 - 环辛二烯，cot = 1,3,5 - 环辛三烯）在[Zn4O（bdc）3]（MOF - 5；bdc = 1,4 - 苯二甲酸）上的气相负载。随后在3巴和150摄氏度下对MOF - 5多孔结构内吸附的配合物进行氢解，得到典型尺寸范围为1.5 - 1.7纳米的钌纳米颗粒，嵌入完整的MOF - 5基质中，这通过透射电子显微镜（TEM）、选区电子衍射（SAED）、粉末X射线衍射（PXRD）和X射线吸收光谱（XAS）得到证实。通过红外光谱跟踪了CO分子在所得Ru@MOF - 5纳米复合材料上的吸附。固态（2）H NMR测量表明，与尺寸相似的表面活性剂稳定的胶体Ru纳米颗粒相比，表面Ru - D物种具有惊人的高迁移率，由此推断MOF - 5是一种具有与嵌入颗粒弱相互作用的稳定载体。令人惊讶的是，[Ru（cod）（cot）]3.5@MOF - 5包合物在25摄氏度的温和条件下进行氢解不会导致Ru纳米颗粒的定量形成。相反，如（13）C MAS NMR、PXRD和TEM所示，会形成一种与骨架bdc连接体的芳烃部分结合的钌 - 环辛二烯配合物。
