Dissolution Behavior and Varied Mesoporosity of Zeolites by NH<sub>4</sub>F Etching
Zhengxing Qin, Zhenchao You, Krassimir N. Bozhilov, Stefan K. Kolev, Wei Yang, Yanfeng Shen, Xin Jin, Jean‐Pierre Gilson, Svetlana Mintova, Georgi N. Vayssilov, Valentin Valtchev
Abstract
Abstract The mesopores formation in zeolite crystals has long been considered to occur through the stochastic hydrolysis and removal of framework atoms. Here, we investigate the NH 4 F etching of representative small, medium, and large pore zeolites and show that the zeolite dissolution behavior, therefore the mesopore formation probability, is dominated by zeolite architecture at both nano‐ and sub‐nano scales. At the nano‐scale, the hidden mosaics of zeolite structure predetermine the spatio‐temporal dissolution of the framework, hence the size, shape, location, and orientation of the mesopores. At the sub‐nano scale, the intrinsic micropore size and connectivity jointly determine the diffusivity of reactant and dissolved products. As a result, the dissolution propensity varies from removing small framework fragments to consuming nanodomains and up to full digestion of the outmost part of zeolite crystals. The new knowledge will lead to new understanding of zeolite dissolution behavior and new adapted strategies for tailoring hierarchical zeolites.