Co ₁ /Ru Single‐Atom Alloy Catalyst for Sustainable Polypropylene Hydrogenolysis to Long‐Chain Liquid Products

Abstract

ABSTRACT Achieving selective polyolefin waste hydrogenolysis into fuels and chemicals requires architectures that disrupt Ru─Ru ensembles without compromising the intrinsic activity of the state‐of‐the‐art Ru catalyst. While metal modifiers can beneficially tune selectivity, they have been shown for high promoter‐metal contents, with associated penalties in structural definition and potential practicality. Here, we engineer cobalt speciation on Ru through impregnation to disclose how promotion spans the entire compositional space realizing a titania‐supported Co 1 /Ru single‐atom alloy catalyst (Co 10 Ru 90 , 3 mol% total metal content) that resolves these trade‐offs. Ex situ and operando analyses reveal that these bimetallic ensembles containing Ru─Co─Ru sites display a distinctively high barrier for over‐hydrogenolysis at late reaction stages while preserving the intrinsic activity of Ru. As a result, virgin polypropylene and post‐consumer waste were almost fully converted with a consistently high C 11+ yield of up to 60% (78% total liquids), compared to <5% over the monometallic Ru counterpart. Process‐level simulations predict economically viable and environmentally sustainable operation enabled by the high single‐pass yields of long‐chain liquid products. These results reveal a wide compositional landscape for Ru promotion and recommend its second‐metal‐content single‐atom alloy limit as the most promising strategy for further catalyst design efforts.