Valence state of chromium in active centers of a potassia-chromia-alumina dehydrogenation catalyst

Abstract

Ni–Cu/SiO2 xerogel catalysts have been synthesized by cogelation of industrial tetraethoxysilane (Dynasil) and chelates of Ni and Cu with industrial 3-(2-aminoethylamino)propyltrimethoxysilane (Dynasylan DAMO) in industrial ethanol denatured with diethyl phthalate. Despite the use of industrial grade reagents, highly dispersed bimetallic Ni–Cu/SiO2 xerogel catalysts were obtained. These samples are composed of completely accessible Ni–Cu alloy crystallites with sizes of 1.6–3.4 nm located inside silica particles exhibiting a monodisperse microporous distribution. It appears that the bimetallic complex acts as a nucleation agent in the formation of silica particles. The combination of results obtained from the calculation of the metal ratio in catalysts, H2 chemisorption and transmission electron microscopy allowed calculating the surface composition of the nickel–copper particles in Ni–Cu/SiO2 cogelled xerogel catalysts. Values obtained indicate a very pronounced surface enrichment with copper. While 1,2-dichloroethane hydrodechlorination over pure nickel mainly produces ethane, increasing copper content in bimetallic catalysts results in an increase in ethylene selectivity. The specific consumption rate of 1,2-dichloroethane decreases when copper loading increases. The turnover frequency, that is, the number of catalytic cycle per active site (nickel atom and its surrounding copper atoms) and per second, seems to be independent of surface composition of alloy particles.