Ru–Zn/ZrO2 Nanocomposite Catalysts Fabricated by Galvanic Replacement for Benzene Partial Hydrogenation

A strategy based on galvanic replacement between metallic Zn and Ru salt followed by acid treatment was developed to fabricate supported Ru–Zn/ZrO2 nanocomposite catalysts with controlled contents of Zn for the benzene partial hydrogenation to cyclohexene. The catalysts were systematically characterized by techniques such as extended X‐ray absorption fine structure, X‐ray photoelectron spectroscopy, and transmission electron microscopy. In benzene partial hydrogenation, with the decrease in the content of Zn, the turnover frequency (TOF) of benzene increased monotonically, whereas the selectivity to cyclohexene evolved in a volcanic trend, passing through a maximum of 72 %. Kinetic analysis indicated that with the depletion of Zn, the rate constant for benzene hydrogenation to cyclohexene and that for cyclohexene hydrogenation to cyclohexane increased simultaneously, but the extents of the increments were at variance. It was identified that the ratios of the rate constants were in parallel with the change in the selectivity to cyclohexene, which is attributed to the electronic effect of metallic Zn that modifies the interactions of Ru with benzene and cyclohexene. Critical zinc: Bimetallic Ru–Zn/ZrO2 nanocomposite catalysts with controlled Zn contents are fabricated by the novel strategy of galvanic replacement between metallic Zn and Ru salt followed by acid treatment. The catalysts feature high cyclohexene selectivity and excellent stability in the industrially significant reaction of benzene partial hydrogenation.