3D-printed monolithic ZSM-5@nano-ZSM-5: Hierarchical core-shell structured catalysts for enhanced cracking of polyethylene-derived pyrolysis oils

The catalytic upgrading of polyethylene-derived pyrolysis oils using ZSM-5 zeolites enables the cost-effective production of valuable chemicals from plastic waste, fostering a circular economy through resource recycling. To achieve high-performance catalyst design, balancing active site accessibility and selectivity is crucial. Here, we report a monolithic ZSM-5 @nano-ZSM-5 core-shell catalyst (mZ@nZ) fabricated via vat photo-polymerization, in situ crystal engineering, and a one-step desilication-recrystallization treatment. The micro -morphologies and microstructures of the core-shell catalysts are investigated using electron microscopies and physical adsorption methods. The mZ@nZ catalyst features a self-supporting face-centered cubic macrostructure with a layer of compositionally heterogeneous ZSM-5 zeolites, which comprises a catalytically benign nano-ZSM-5 shell (Si-rich) and a catalytically active ZSM-5 core (Al-rich). Abundant mesopores are created in mZ@nZ through desilication and zeolite agglomeration processes. This design offers three significant advantages: (1) enhanced active site accessibility via in situ zeolite growth, (2) surface passivation using a Si-rich shell to minimize side reactions, and (3) improved diffusion facilitated by the hierarchical structure, reducing light olefin secondary reactions and coke formation. Compared to pristine monolithic ZSM-5 and a reference pelletized catalyst, the mZ@nZ catalyst demonstrates superior performance in terms of higher light olefin yields and se-lectivities, with enhanced resistance to coking in the model compound and real LDPE pyrolysis oil cracking reactions. This research showcases a rational design approach at both macroscopic and microscopic scales, of-fering valuable insights for advancing polyolefin waste upgrading and novel zeolite catalyst design.