Data-Driven Discovery of Bimetallic Nanoparticles Catalysts for the Hydrogenolysis of Polyethylene

Supported platinum nanoparticles are known to convert polyolefins to high-quality liquid hydrocarbons with hydrogen under relatively mild conditions. However, no systematic study has been undertaken using bimetallic catalysts for polyethylene upcycling. Specifically, a total of 98 monometallic and bimetallic combinations (Ag, Cr, Co, Cu, Fe, Ga, In, Mn, Ni, Pd, Pt, Rh, Ru, Zr) on alumina were synthesized utilizing surface organometallic chemistry (SOMC) technique via robotic platform. These were investigated at a small scale (10 mg of catalyst and 50 mg of polyethylene) for their activity for the hydrogenolysis of polyethylene in a high-throughput batch reactor. Combinations of Ni and Co were selected as candidates with high activity toward conversion into paraffin oils. Reaction conditions were optimized with Ni/Co/Al2O3 catalyst at a larger scale (300 mg catalyst and 3 g polyethylene) to obtain a high yield (93.1%) of paraffin wax with desired properties (Mn = 380 Da) and low polydispersity (Đ = 1.2). Ni/Co/Al2O3 was compared against Co/Ni/Al2O3 to understand the role of the deposition sequence. When Co is deposited before Ni, a layer of cobalt aluminate is formed upon reduction, stabilizing the deposition of 5 nm metallic Ni particles. When nickel is deposited before Co, particles are larger (average >20 nm) and more oxidized (Niδ+ in NiAl2O4), decreasing the availability of the catalytically active metallic Ni. The difference in electronic environments was also described by DFT calculations, which revealed that smaller 3D clusters of Ni are preferred on CoAl2O4 over the 3D clusters on NiAl2O4 and that these smaller clusters are more reducible, as confirmed experimentally.