Entropy-Governed Zeolite Intergrowth

Entropy, stemming from the second law of thermodynamics, drives the system toward greater disorder. In zeolite design, introducing controlled disorder enhances mass transfer, yet most strategies focus on regulating structure from the perspective of energy, with few efforts devoted to entropy effect control. Here, we propose an entropy strategy by enhancing the translational and rotational confinement of large organic structure-directing agents (OSDAs), leading to an order of magnitude larger change in free energy (1.8 kJ/mol SiO₂) than the enthalpy effect. This in turn promotes compensation in the configurational entropy of zeolite structures, leading to the formation of highly disordered intergrown zeolites (e.g., ITH/ITR, MFI/MEL, etc.). Our entropy strategy paves a novel perspective for the intergrowth of zeolites, holding significant guidance for the microscopic mechanisms underlying the formation of zeolite skeletons, including highly disordered porous materials.