Microstructure control of magnesium dichloride crystallites by electron donors: The effect of methanol

The Influence of Alcohols in Driving the Morphology of Magnesium Chloride Nanocrystals

“…According to DFT‐D calculations, in the presence of adsorbates a huge stabilization of all the surfaces occurs. In particular, both alcohols selectively stabilize the (1 1 0) surface with respect to naked MgCl 2 , in agreement with the recent literature . Our systematic computational approach allows relevant differences between methanol and ethanol to be appreciated.…”

“…Since the 1980s, ZN catalysts have been traditionally investigated by means of molecular mechanics and quantum‐mechanical computations aimed at identifying possible reaction mechanisms for olefin polymerization on what were supposed to be the most stable MgCl 2 surfaces in the presence of LBs and Ti x Cl 4− x . In the last decade, the application of DFT and DFT methods including dispersion (DFT‐D) to elucidate the energetics of the interaction and the local structures of TiCl 4 (or Ti x Cl 3 x ) and the LB at these surfaces substantially renewed the seminal vision of catalysis on MgCl 2 . Recent simulations performed on clusters of different sizes and morphologies demonstrated that the relative stabilities of the MgCl 2 surfaces drastically change in the presence of donors.…”

“…In the last decade, the application of DFT and DFT methods including dispersion (DFT‐D) to elucidate the energetics of the interaction and the local structures of TiCl 4 (or Ti x Cl 3 x ) and the LB at these surfaces substantially renewed the seminal vision of catalysis on MgCl 2 . Recent simulations performed on clusters of different sizes and morphologies demonstrated that the relative stabilities of the MgCl 2 surfaces drastically change in the presence of donors. This holds for several small donor molecules (e.g., H 2 O, NH 3 , methanol, ethanol), as well as for the industrially employed donors .…”

“…Recent simulations performed on clusters of different sizes and morphologies demonstrated that the relative stabilities of the MgCl 2 surfaces drastically change in the presence of donors. This holds for several small donor molecules (e.g., H 2 O, NH 3 , methanol, ethanol), as well as for the industrially employed donors . Interestingly, these theoretical studies validated the experimental results obtained years before by Thune and co‐workers on a planar model of MgCl 2 , by which the effect of an internal donor in controlling the morphology of the MgCl 2 crystals formed during the preparation of a ZN catalyst was visualized for the first time.…”

MgCl2‐supported Ziegler‐Natta catalysts: A DFT‐D ‘flexible‐cluster’ approach. TiCl4 and probe donor adducts

“…Computational modeling is one of the pillars of the mechanistic investigation. Over the last four decades, the modeling approach has evolved from pioneering applications of Molecular Mechanics to Density Functional Theory (DFT) calculations corrected for dispersion interactions (DFT‐D) . Our group was the first to come up with a realistic description of TiCl 4 chemisorption on MgCl 2 crystal surfaces using periodic DFT‐D codes .…”