Gate-Tailoring with Protons and Metal Cations in a Flexible Zeolite for High-Efficiency Ethylene/Ethane Separation

作者：Xiaohe Wang, Libo Li, Nana Yan, Lei Wang, Reisel Millán, Puxu Liu, Yueying Chu, Yida Zhou, Wei Gao, Jun Xu, Juping Xu, Wen‐Jin Yin, Yuan Bao, Zhenduo Wu, Avelino Corma, Shutao Xu, Zhongmin Liu, Wenfu Yan, Peng Guo, Jinping Li, Mercedes Boronat, Jihong Yu · 发表于：Journal of the American Chemical Society · 年份：2026 · DOI：10.1021/jacs.6c06425 · 被引用次数：1 · 研究领域：Zeolite Catalysis and Synthesis、Catalytic Processes in Materials Science

Ethylene/ethane separation underpins global polyolefin production but remains one of the most energy-intensive processes in the chemical industry because it relies on cryogenic distillation. Adsorptive separation using porous materials offers a promising alternative to conventional cryogenic distillation, potentially reducing energy consumption. However, the nearly identical physical properties of ethylene and ethane make the development of highly selective adsorbents exceptionally challenging. Herein, we report a lithium-exchanged silicoaluminophosphate RHO zeolite (Li-SAPO-RHO) that achieves unprecedented ethylene/ethane separation by exploiting a cooperative gating mechanism in a flexible framework. A synergistic proton-Li + gating effect at the flexible 8-ring apertures differentially modulates molecular transport barriers. Brønsted protons selectively facilitate ethylene diffusion, while Li + cations create a trapdoor barrier that preferentially suppresses ethane transport, thereby amplifying kinetic discrimination. As a result, Li-SAPO-RHO exhibits excellent ethylene-selective adsorption performance, enabling the direct production of polymer-grade ethylene (>99.9%) from refinery dry gas with a productivity of 238.6 mmol/L. Structural analyses combined with ab initio molecular dynamics simulations reveal how proton–cation synergy amplifies kinetic discrimination between closely related molecules. These findings establish gate cooperativity as a powerful design principle ...