Hydrogenolysis of alkanes and olefin polymerization on the silica-supported zirconium hydrides: A comparative DFT study

The model reactions of ethylene polymerization and hydrogenolysis of linear alkanes (propane, n-butane, and n-pentane) on the silica-supported zirconium hydrides (Si–O)₃Zr^IVH, (Si–O)₂Zr^IVH₂, and (Si–O)₂Zr^IIIH were studied using the DFT approach. Catalytic processes under study were shown to occur involving different surface hydrides. The ethylene polymerization was found to proceed at comparable rates on the zirconium monohydrides, (Si–O)₃ZrH, and dihydrides, (Si–O)₂ZrH₂. Cleavage of linear alkanes on the monohydrides (Si–O)₃ZrH is thermodynamically unfavorable; however, the dihydrides (Si–O)₂ZrH₂ can act as catalysts of the process under mild conditions. Hydrides of the trivalent zirconium, (Si–O)₂Zr^IIIH, can also contribute to the hydrogenolysis reaction. A feature of all the systems studied is low regioselectivity of the corresponding processes.