Details

Autor(en) / Beteiligte

• Jongkind, Maarten K.
• Rivera‐Torrente, Miguel
• Nikolopoulos, Nikolaos
• Weckhuysen, Bert M.

Titel

Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks

Ist Teil von

• Chemistry : a European journal, 2021-03, Vol.27 (18), p.5769-5781

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2021

Link zum Volltext

Quelle

Wiley Online Library Journals Frontfile Complete

Beschreibungen/Notizen

• Metal–organic frameworks (MOFs) have received increasing interest as solid single‐site catalysts, owing to their tunable pore architecture and metal node geometry. The ability to exploit these modulators makes them prominent candidates for producing polyethylene (PE) materials with narrow dispersity index (Ð) values. Here a study is presented in which the ethylene polymerization properties, with Et2AlCl as activator, of three renowned Cr‐based MOFs, MIL‐101(Cr)‐NDC (NDC=2,6‐dicarboxynapthalene), MIL‐53(Cr) and HKUST‐1(Cr), are systematically investigated. Ethylene polymerization reactions revealed varying catalytic activities, with MIL‐101(Cr)‐NDC and MIL‐53(Cr) being significantly more active than HKUST‐1(Cr). Analysis of the PE products revealed large Ð values, demonstrating that polymerization occurs over a multitude of active Cr centers rather than a singular type of Cr site. Spectroscopic experiments, in the form of powder X‐ray diffraction (pXRD), UV/Vis‐NIR diffuse reflectance spectroscopy (DRS) and CO probe molecule Fourier transform infrared (FTIR) spectroscopy corroborated these findings, indicating that indeed for each MOF unique active sites are generated, however without alteration of the original oxidation state. Furthermore, the pXRD experiments indicated that one major prerequisite for catalytic activity was the degree of MOF activation by the Et2AlCl co‐catalyst, with the more active materials portraying a larger degree of activation. Multiple active sites: MIL‐101(Cr)‐NDC, MIL‐53(Cr) and HKUST‐1(Cr) were tested for ethylene polymerization and found to produce different polyethylene (PE) products and PE morphologies. Analysis of the PE revealed that multiple active sites exist, indicating that the active phase cannot be considered a single‐site catalyst. An array of spectroscopic techniques was used to investigate active site formation for the aforementioned metal–organic frameworks (MOFs).