Interfacial Engineering of Zeolite-Based Multicomponent Catalysts Enables Synergistic Acid−Diffusion Coupling for Efficient Polyolefin Upcycling

Abstract Advancing catalytic materials and processes to meet evolving social and industrial demands is a central pursuit in catalysis. Industrial zeolite catalysts are inherently multicomponent systems, in which active zeolitic components are intimately integrated with nonzeolitic components (e.g., SiO2, Al2O3, or amorphous silica-alumina, ASA). These nonzeolitic components are indispensable for ensuring mechanical stability and process compatibility, and they actively participate in the pre-cracking of polyolefin. However, the interactions between these components remain critical yet poorly understood, creating a gap between fundamental research and practical catalyst design, which still relies heavily on empirical approaches. In this work, we investigate how the nonzeolitic component reshapes the zeolitic interface, revealing the fundamental principles governing intercomponent interactions. We construct a hierarchical ZSM-5/ASA integrated catalyst via a “waste-to-resource” strategy that utilizes alkaline post-treatment effluents, thereby mitigating wastewater discharge. We elucidate how the ASA component fundamentally alters the zeolitic microenvironment. Through multidimensional solid-state NMR and complementary spectroscopic analyses, we demonstrate that nanoscale proximity induces dynamic interfacial aluminum migration, generating highly accessible Brønsted acid sites at the heterointerface. Coupled with a cooperative mesopore network, these sites establish an acidity-diffusion gradient that synchronizes the pre-cracking of bulky hydrocarbons with the deep cracking of intermediates. By tracing the spatiotemporal evolution of intermediates and coke, this work provides molecular-level insights into the interplay between reaction and diffusion in multicomponent catalysts. It establishes a mechanism-guided paradigm for catalyst design, demonstrating that rational control of interfacial acid-diffusion synergy enables efficient polyolefin upcycling while minimizing environmental impacts.