Li Botian, Zhou Xue, Liu Xiangyun, Ye Haimu, Zhang Ying, Zhou Qiong
Department of Materials Science and Engineering, China University of Petroleum, Beijing, 102249, P. R. China.
Chem Asian J. 2019 May 2;14(9):1582-1589. doi: 10.1002/asia.201900131. Epub 2019 Apr 10.
Metal-organic gels showing potential application in catalysis have received much concern. In this work, we designed and synthesized two metal-organic gels based on coordination between Fe and pyridine ligands at room temperature. The gels were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to reveal their assembly structures and morphologies, and it was found the metal-organic gel derived from di-topic ligand was composed of three-dimensional network of nanofibers, while the gel derived from tri-topic ligand was constituted of sponge-like structure with amorphous phase. Rheological analysis showed the gel consisting of nanofiber networks displayed self-healing property. The gels were used as catalysts for selective ethylene dimerization, and the optimum catalysis results of the gel with nanofibers reached the maximal catalytic activity of 1.48×10 g/(mol Fe⋅h) with C yield more than 90 %, whereas the sponge-like gel only gave 38 % C products at the same condition. The higher dimerization selectivity of the former Fe gel was attributed to its regular assembly structure and lower steric hindrance of the surface metal sites. Due to its catalytic activity, high selectivity and preparation simplicity, the Fe gel might be potentially applicable for the preparation of C α-olefins.
在催化领域展现出潜在应用价值的金属有机凝胶受到了广泛关注。在本工作中,我们在室温下基于铁与吡啶配体之间的配位作用设计并合成了两种金属有机凝胶。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对凝胶进行表征,以揭示其组装结构和形态,结果发现由双齿配体衍生的金属有机凝胶由三维纳米纤维网络组成,而由三齿配体衍生的凝胶则由具有非晶相的海绵状结构构成。流变学分析表明,由纳米纤维网络组成的凝胶具有自愈性能。这些凝胶被用作选择性乙烯二聚反应的催化剂,具有纳米纤维的凝胶的最佳催化结果达到了最大催化活性1.48×10 g/(mol Fe⋅h),C产物收率超过90%,而在相同条件下,海绵状凝胶的C产物仅为38%。前一种铁凝胶较高的二聚选择性归因于其规则的组装结构和表面金属位点较低的空间位阻。由于其催化活性、高选择性和制备简便性,铁凝胶可能潜在地应用于Cα-烯烃的制备。