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, herein, we describe the application of Li-ion battery 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 (LixMn(2)O(4)) to yield isolated Ni2+ occupying the vacant interstitial octahedral site in the Li diffusion channel on the surface and subsurface of the spinel structure (Ni/LixMn(2)O(4)). The activity of Ni/LixMn(2)O(4) for olefin hydrogenation, as a representative probe reaction, was found to increase monotonically as a function of support reductive lithiation. Simulation of Ni/LixMn(2)O(4) reveals the dramatic impact of surface redox states on the viability of the homolytic oxidative addition mechanism for H-2 activation. Catalyst control through support lithiation was extended to an organotantalum complex on LixTiO(2), demonstrating the generality of this phenomenon.

Automated summary

This article describes the application of Li-ion battery cathode and anode materials as redox non-innocent catalyst supports for the electronic tuning of a catalyst's active site. The activity of the catalyst for olefin hydrogenation was found to increase as a function of support reductive lithiation. Simulation results reveal the significant impact of surface redox states on the viability of the homolytic oxidative addition mechanism.