Lithium Ion Battery Materials as Tunable, Redox Non-Innocent Catalyst Supports

The development of general strategies for the electronic tuning of a catalyst’s active site is an ongoing challenge in heterogeneous catalysis. To this end we report the application of cathode and anode materials as redox non-innocent catalyst supports that can be continuously modulated as a function of lithium intercalation. A zero valent nickel complex was oxidatively grafted onto the surface of lithium manganese oxide (Li_xMn₂O₄) to yield single-sites of Ni²_­⁺ (Ni/Li_xMn₂O₄). Its activity for olefin hydrogenation was found to be a function of the redox state of the support material, with the most lithiated variant showing the most activity. X-ray absorption, X-ray photoelectron, solid-state nuclear magnetic resonance and electron paramagnetic resonance spectroscopies, and electron microscopy techniques established the nature of the nickel species on Li_xMn₂O₄. Catalyst control through support redox non-innocence was extended to an organotantalum complex on lithium titanium oxide (Li_xTiO₂), demonstrating the generality of this phenomenon.