Activated MgCl2 nanocrystals were prepared by controlled dealcoholation of the MgCl2·6CH3OH adduct, mimicking the routinely adopted methods to synthesize industrial heterogeneous Ziegler–Natta catalysts. The effect of the alcohol in driving the morphology of MgCl2 crystals, i.e., the type and extension of the exposed surfaces, was investigated by integrating a detailed structural, morphological, and surface characterization with a state-of-the-art computational modeling. FT-IR spectroscopy of CO adsorbed at 100 K emerged as a feasible, simple, and powerful method to characterize the surface of structurally disordered MgCl2 and MgCl2-based Ziegler–Natta catalysts. Our computational morphological analysis revealed that the (012), (015), and (110) surfaces are highly stabilized by methanol as an electron donor, especially at the temperature typically adopted in the preparation of the precatalysts. FT-IR spectroscopy of adsorbed CO allows distinguishing these surfaces from the other penta-coordinated ones and provides a clear experimental evidence that TiCl4 binds to the (110) and (015) surfaces. The (015) surface was never considered in the past and is characterized by an unusual flexibility in the presence of adsorbates, which detach the Mg cations from the Cl underneath, leaving a coordination vacancy available for the binding of asymmetric titanium sites. Since the recent literature identified a tetra-coordinated Mg as a site of election for the deposition of the Ti species relevant in olefin polymerization, the presence of two eligible Mg sites for Ziegler–Natta catalysis is highly interesting.

Two Ziegler−Natta catalysts supported on molecularadducts, namely, MgCl2·6EtOH (ME) and MgCl2·5EtOH·EtOOCPh (Est-ME), have been prepared. A systematic effort has been made to unravel the molecular level structure−property relationships of the catalysts and adducts. Ethylbenzoate is an internal electron donor, and its in situ formation through EtOH + PhCOCl coupling is successfully achieved. The above adduct has been treated with TiCl4, and the resultant catalyst (Ti/Est-ME) is evaluated for ethylene polymerization activity. IR and 13C CP/MAS NMR of Est-ME (Ti/Est-ME) show carbonyl features at 1730 (1680) cm−1 and 169 (170) δ, respectively, providing direct support for the presence of ester as an integral part. In spite of low surface area, Ti/Est-ME gives higher yield for ethylene polymerization than the one derived from ME. The results indicate that electronic environment is more important than surface area or any other single factor in determining the polymerization activity.

Solid solutions of GaN in ZnO (Zn 1-z Ga z )(O 1-x N x ) (x and z e 0.15) have been prepared by simple solution combustion method. Except for minor changes in the lattice contraction, no significant change in the Wurtzite structure was observed. Raman and secondary ion mass spectrometry results show the direct Zn-N and Ga-N bonds in (Zn 1-z Ga z )(O 1-x N x ). Visible light absorption and XPS results demonstrate that N 2p states of nitride occupy the states above the O 2p valence band, and hence a change in optical band gap reduction occurs to ∼2.5 eV from 3.37 eV for ZnO. Significant nitrogen fixation catalytic activity through NH 3 formation has been observed at ambient pressure on virgin (Zn 1-z Ga z )(O 1-x N x ) material, indicating its potential as a catalyst.

A new molecular adduct, MgCl 2 · 4(CH 3 ) 2 CHOH, has been synthesized and characterized for structural aspects and demonstrated for super active ethylene polymerization activity with TiCl 4 to ultrahigh molecular weight polyethylene in high yield.