Structure–Property Relationships for Nickel Aluminate Catalysts in Polyethylene Hydrogenolysis with Low Methane Selectivity

[Image: see text] Earth-abundant metals have recently been demonstrated as cheap catalyst alternatives to scarce noble metals for polyethylene hydrogenolysis. However, high methane selectivities hinder industrial feasibility. Herein, we demonstrate that low-temperature ex-situ reduction (350 °C) of coprecipitated nickel aluminate catalysts yields a methane selectivity of <5% at moderate polymer deconstruction (25–45%). A reduction temperature up to 550 °C increases the methane selectivity nearly sevenfold. Catalyst characterization (XRD, XAS, (27)Al MAS NMR, H(2) TPR, XPS, and CO-IR) elucidates the complex process of Ni nanoparticle formation, and air-free XPS directly after reaction reveals tetrahedrally coordinated Ni(2+) cations promote methane production. Metallic and the specific cationic Ni appear responsible for hydrogenolysis of internal and terminal C–C scissions, respectively. A structure-methane selectivity relationship is discovered to guide the design of Ni-based catalysts with low methane generation. It paves the way for discovering other structure–property relations in plastics hydrogenolysis. These catalysts are also effective for polypropylene hydrogenolysis.