A single phase molecular adduct, MgCl2·6CH3OH has been synthesized using MgCl2 and the simplest alcohol, methanol. Structural, spectroscopic, and morphological studies have been carried out for a better understanding of the single phase MgCl2·6CH3OH adduct. 13C CPMAS solid state NMR studies show all six methanol molecules are magnetically equivalent and present in a single environment around the Mg2+ center. Raman spectral analysis of the characteristic peak at 708 cm–1 substantiates octahedral coordination of six CH3OH molecules around Mg2+. Solid state 13C NMR measurements, made after heat treatment at different temperatures, have been utilized to understand the variations in CH3OH stoichiometry and coordination around Mg2+ with temperature. A titanated active catalyst, TiCl4 on MgCl2·6CH3OH, has also been synthesized and subjected to detailed characterizations. The active catalyst shows high surface area (102 m2/g) and mesoporosity. The titanated catalyst has been screened for ethylene polymerization reactions using different cocatalysts (R3Al; R= −CH3, −CH2CH3, and −CH2CH(CH3)2). A total of 7.25 kg of polyethylene per gram of catalyst has been obtained with Me3Al cocatalyst, which is six times higher in activity compared with commercial Me3Al/TiCl4/ MgCl2·6EtOH-supported catalyst. Although porosity influences the catalytic activity, other factors also seem to contribute to the total catalytic activity.

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.

Dehydrogenation or oxidative dehydrogenation (ODH) of alkanes to produce alkenes directly from natural gas/shale gas is gaining in importance. Ti3AlC2, a MAX phase, which hitherto had not been used in catalysis, efficiently catalyzes the ODH of n‐butane to butenes and butadiene, which are important intermediates for the synthesis of polymers and other compounds. The catalyst, which combines both metallic and ceramic properties, is stable for at least 30 h on stream, even at low O2:butane ratios, without suffering from coking. This material has neither lattice oxygens nor noble metals, yet a unique combination of numerous defects and a thin surface Ti1−yAlyO2−y/2 layer that is rich in oxygen vacancies makes it an active catalyst. Given the large number of compositions available, MAX phases may find applications in several heterogeneously catalyzed reactions.

A simple and highly efficient surfactant-free sol-gel process has been developed to obtain nanocrystalline mesoporous g-Al 2 O 3 and metal ion incorporated mesoporous g-Al 2 O 3 with general formula g-Al 2Àx M x O 3AEy (where M ¼ Ti 4+ through Ga 3+ ). Any one of the first row transition metal (TM) ions along with Ga 3+ could be introduced into the g-Al 2 O 3 framework in a direct one-pot synthesis process. The generality of the present synthesis recipe for metal ion incorporation in g-Al 2 O 3 was demonstrated by preparation of an Al-Ga-M ternary oxide system with the metal ion composition of general formula Al 9 GaTM (TM ¼ Ti 4+ to Zn 2+ ) and their characterization through various physicochemical and spectroscopic techniques. The mesoporous g-Al 2Àx M x O 3AEy materials showed a BET surface area in the range of 200-400 m 2 g À1 with a narrow pore size distribution. Wormhole mesoporosity makes the material pseudo-3D (p3D) with a small pore depth of few nm (<10 nm). Metal ions in g-Al 2 O 3 lead to changes in the acidity and electronic environment. XRD, TEM, and 27 Al MAS NMR studies demonstrate that the sol-gel process and the disordered mesoporous structure allow Ga and TM ions to be highly distributed and integrated in the g-Al 2 O 3 framework. The efficacy of these materials in catalysis has been successfully evaluated for steam reforming of dimethylether: Ni, Cu and Zn containing Al 9 GaTM oxides showed high activity and stability. The smaller mesochannel depth (<10 nm) and pseudo-3D characteristics that arise due to the wormhole-type disordered mesoporous framework of these alumina materials facilitate mass transport through them without any leaching of metal ions out of the lattice and pore blocking during the reaction, which makes them attractive in catalysis. This preparation method is versatile enough to be used for a reproducible synthesis of metal ion incorporated mesoporous g-Al 2 O 3 by varying the metal content and their combinations, and it is expected that many other metal ions could be introduced into the lattice framework for a variety of applications by tuning acidity and electronic structure.

Lattice matching holds the secret to the Ru-catalysed hydrogenation of xylose to xylitol, a key reaction in practical biomass conversion.