Size-inverse molecular sieving xenon/krypton separation through cation-tuned gating effect within Linde Type A zeolites

Achieving highly selective xenon/krypton separation is a longstanding challenge due to the similar physicochemical properties of these noble gases. Here, we develop the cation-tuned gating sieving mechanism in Linde Type A zeolites to achieve a high xenon/krypton IAST selectivity over 1600. Through the cation exchange by Ag+ to introduce the preferential binding of xenon over krypton gas, followed by Ca²⁺ exchange to modulate cation density within the pore cavity so as to facilitate xenon uptake, the resulting Ag9Ca1.5A overcomes the kinetic limitations and achieves a dynamic xenon/krypton selectivity of 30 — the highest reported in the open literature — along with a high dynamic xenon uptake of 1.65 mmol/g. In this work, the sieving separation mechanism is exclusively established by the combined isothermal adsorption measurements, breakthrough experiments, synchrotron powder X-ray diffraction, X-ray absorption spectra, and ab initio density functional theory calculations. Zeolite with silver-tuned gating achieves counterintuitive size-inverse sieving, delivering record xenon/krypton separation and a scalable, energy-efficient path for challenging gas separations.