Formation of Active Centers of Nickel–Zinc Catalysts Deposited on the Nanodiamond for the Selective Hydrogenation of Phenylacetylene

Abstract

A study is performed of bimetallic catalysts NiZn/ND with ratios Ni : Zn = 1 : 1 and 1 : 3 prepared by impregnation using detonation nanodiamond (ND) as a support. They were compared with monometallic Ni/ND and Zn/ND. It is shown by nitrogen adsorption/desorption, scanning and transmission electron microscopy that metal deposition does not affect the porous structure or morphology of a support. Coordination of metal precursors on a nanodiamond surface proceeds with the participation of functional groups, as is confirmed by a change in the electrokinetic charge of the surface. The reduction of metal precursors is studied by temperature-programmed reduction and in situ XAFS spectroscopy. In Ni-containing samples, two forms of Ni2+ are found that are bonded differently with the support. ZnO is not reduced in the samples upon treatment with hydrogen at temperatures up to 400°C. The fraction of reduced nickel is determined by analyzing XANES spectra. Virtually full reduction of nickel is observed in a catalyst with a Ni : Zn ratio of 1 : 1 after 4 h of in situ treatment with hydrogen inside a spectrometer cell at 400°C, but not at a Ni : Zn ratio of 1 : 3 under the same conditions. The highest selectivity of styrene formation in the reaction of phenylacetylene hydrogenation throughout the investigated range of temperatures (100–350°С) is ensured by NiZn/ND; NiZn3/ND is less active and selective, since ZnO closes the active nickel centers and prevents the adsorption of phenylacetylene.