Cyclohexane oxidative dehydrogenation over copper oxide catalysts

Here, we report on structure-reactivity trends for cyclohexane oxidative dehydrogenation (ODH) with silica supported copper oxide catalysts as a function of surface structure. Copper oxide was supported on mesostructured KIT-6 silica at low surface densities <0.2 Cu/nm² using copper (II) nitrate, ammonium and sodium copper (II) ethylenediaminetetraacetate, and a hexanuclear copper (I) siloxide complex. Copper oxide surface structures were characterized by X-ray absorption spectroscopy as well as ambient and in situ diffuse reflectance UV–visible (DRUV–vis) spectroscopy to determine trends in copper oxide nuclearity. DRUV–vis spectroscopy identifies three copper species based on Cu²⁺ ligand to metal transfer (LMCT) bands at 238, 266, and >300 nm as well as Cu⁺ LMCT bands at 235, 296, and 312 nm. Counterintuitively, EXAFS analysis shows that the multinuclear precursor leads to fewer average Cu–Cu interactions than syntheses with mononuclear copper salt precursors. Turnover frequency and selectivity to benzene increase with decreasing copper oxide nuclearity, and thus the multinuclear precursor leads to the highest turnover frequency and benzene production. This work shows the variety of surface species that exist even at extremely low copper surface densities, control of which can improve reactivity of an atypical ODH catalyst up to rates comparable to benchmark vanadia catalysts.