Shibashish D. Jaydev

Catalytic hydrogenolysis has the potential to convert high‐density polyethylene (HDPE), which comprises about 30 % of plastic waste, into valuable alkanes. Most investigations have focused on increasing activity for lab grade HDPEs displaying low molecular weight, with limited mechanistic understanding of the product distribution. No efficient catalyst is available for consumer grades due to their lower reactivity. This study targets HDPE used in bottle caps, a waste form generated globally at a rate of approximately one million units per hour. Ultrafine ruthenium particles (1 nm) supported on titania (anatase) achieved up to 80 % conversion into light alkanes (C₁−C₄₅) under mild conditions (498 K, 20 bar H₂, 4 h) and were reused for three cycles. Small ruthenium nanoparticles were critical to achieving relevant conversions, as activity sharply decreased with particle size. Selectivity commonalities and peculiarities across HDPE grades were disclosed by a reaction modelling approach applied to products. Isomerization cedes to backbone scission as the reaction progresses. Within this trend, low molecular weight favor isomerization whilst high molecular weight favor cleavage. Commercial caps obeyed this trend with decreased activity, anticipating the influence of additives in realistic processing. This study demonstrates effective hydrogenolysis of consumer grade polyethylene and provides selectivity patterns for product control.

Catalytic hydrogenolysis has the potential to convert high‐density polyethylene (HDPE), which comprises about 30 % of plastic waste, into valuable alkanes. Most investigations have focused on increasing activity for lab grade HDPEs displaying low molecular weight, with limited mechanistic understanding of the product distribution. No efficient catalyst is available for consumer grades due to their lower reactivity. This study targets HDPE used in bottle caps, a waste form generated globally at a rate of approximately one million units per hour. Ultrafine ruthenium particles (1 nm) supported on titania (anatase) achieved up to 80 % conversion into light alkanes (C₁−C₄₅) under mild conditions (498 K, 20 bar H₂, 4 h) and were reused for three cycles. Small ruthenium nanoparticles were critical to achieving relevant conversions, as activity sharply decreased with particle size. Selectivity commonalities and peculiarities across HDPE grades were disclosed by a reaction modelling approach applied to products. Isomerization cedes to backbone scission as the reaction progresses. Within this trend, low molecular weight favor isomerization whilst high molecular weight favor cleavage. Commercial caps obeyed this trend with decreased activity, anticipating the influence of additives in realistic processing. This study demonstrates effective hydrogenolysis of consumer grade polyethylene and provides selectivity patterns for product control.

Efforts to selectively convert polypropylene (≈30 % of all plastic waste) have not been particularly successful. Typical distributions span from gas to solid products, highlighting a challenging cleavage control. Here, carbon‐supported platinum nanoparticles were designed for complete hydrocracking into liquid hydrocarbons (C₅–C₄₅). The metal and carrier phases operated synergistically. The cleavage activity depended on platinum and its rate rose with decreasing particle size. The carbon carrier controlled selectivity via hydrocarbon binding strength, which depended on the chain length and on the surface oxygen concentration. An optimal binding provided by carbons with high oxygen content promoted both adsorption of long chains and desorption of short products. This strategy achieved an unprecedented 80 % selectivity toward motor oil (C₂₁–C₄₅). Carbons exhibiting too strong binding (low oxygen content) hindered product desorption, while non‐binding materials (e. g., silica or alumina) did not promote plastic–Pt contact, leading in both cases to low performance. This work pioneers design guidelines in a key process towards a sustainable plastic economy.