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    Tracing Active Sites in Supported Ni Catalysts during Butene Oligomerization by Operando Spectroscopy under Pressure
    (Washington, DC : ACS, 2016) Rabeah, Jabor; Radnik, Jörg; Briois, Valérie; Maschmeyer, Dietrich; Stochniol, Guido; Peitz, Stephan; Reeker, Helene; La Fontaine, Camille; Brückner, Angelika
    Supported Ni catalysts have been studied during the dimerization of butenes by operando electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) at 353 K and up to 16 bar. Single NiI/NiII shuttles were identified as active sites, whereby the conversion of initial NiI to NiII by oxidative addition of butene is obviously faster than the re-reduction of NiII to NiI by reductive elimination of the C8 product, rendering the equilibrium percentage of NiI small. At p ≤ 2 bar, NiI single sites form inactive Ni0 aggregates, while this is suppressed at higher pressure (∼12 bar). A reaction mechanism is proposed.