The application of the Assembly−Disassembly−Organization−Reassembly (ADOR) protocol to the synthesis of germanosilicate zeolites has become a major milestone in material design by enabling the preparation of previously unknown "isoreticular" zeolites with tunable building units (i.e., -d4r-, -s4r-, -O-) connecting crystalline layers. Two processes operating in the disassembly step, deconstructive "deintercalation" and reconstructive "rearrangement", determine the structure of ADOR-derived zeolites. However, independent management of these key ADOR processes, which would be desirable to regulate the characteristics of the products, has remained elusive thus far. Herein, we report a new method for controlling the primary steps of the ADOR process and present the first example of a "cycled" structural transformation of interlayer units (d4r → s4r → d4r) in the germanosilicate UTL zeolite under "slow deintercalation"/"fast rearrangement" conditions. The "slow deintercalation" mode of ADOR enabled us to prepare the previously known OKO, *PCS, IPC-7 zeolites via gradual reduction of interlayer units in UTL (d4r → d4r/s4r → s4r → s4r/-O-), in contrast to conventional rearrangement-driven synthesis (-O-→ s4r/-O-→ s4r...). X-ray powder diffraction (XRD), sorption, and solid-state NMR time-resolved studies revealed that the "slow deintercalation/fast rearrangement" modification of ADOR makes it possible to adjust the pore architecture of germanosilicate zeolites toward increasing their micropore size, which has never been achieved before in the classical ADOR mechanism. Therefore, "slow deintercalation" or "slow deintercalation/fast rearrangement" routes provide a tool for controlling the "isoreticular" zeolite structure. Ultimately, the results from this study may facilitate the design of previously predicted but inaccessible members of the ADORable zeolite family.

The Assembly-Disassembly-Organisation-Reassembly (ADOR) process has led to the discovery of numerous zeolite structures, albeit limited to materials with decreased pore size in relation to the parent germanosilicate zeolite. This limitation...

The Assembly–Disassembly–Organization–Reassembly (ADOR) process has been used extensively to prepare new zeolite frameworks based on germanosilicate precursors. The disassembly step exploits the lability of the bonds in the presence of water to selectively disconnect the framework, prior to reorganization into new framework topologies. However, a mechanistic understanding of this crucial step is lacking: specifically, the roles of heteroatom (germanium) content and water loading in zeolite hydrolytic instability. In this work, ab initio free energy simulations, coupled with water vapor adsorption measurements reveal that collectivity effects control the reactivity of the archetypal ADORable zeolite UTL toward water. A transition between reversible and irreversible water adsorption occurs as water loading is increased, leading to reactive transformations. Clustering of germanium is observed to activate hitherto unreported favorable hydrolysis mechanisms beyond a threshold concentration of three atoms per double four ring unit, demonstrating that the heteroatom distribution and collectivity in the hydrolysis mechanism can drastically influence zeolite framework instability. These findings suggest that control over heteroatom content, distribution, and hydration level is important to achieve the controlled partial hydrolysis of zeolitic frameworks and is likely to apply not only to other ADORable germanosilicate zeolites but also to Lewis acidic zeolites in general.

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New zeolitic frameworks can be prepared through the Assembly-Disassembly-Organisation-Reassembly (ADOR) process by exploiting the lability of Ge-O bonds in germanosilicate zeolites to control their hydrolysis. In the disassembly step, two key factors are water and germanium content, but their exact roles remain unknown. Nevertheless, we combined experimental water-vapor adsorption with first principles simulations to identify the mechanism of germanosilicate zeolite disassembly. The results showed that water vapor adsorption on <b>UTL</b> germanosilicate proceeds in reversible (at low partial pressures) and irreversible (at higher partial pressures) modes. Based on our ab initio molecular dynamics simulations, we related these two modes to weak physisorption at low water loading and to reactive transformations at high water loading, via collective mechanisms requiring high local water concentrations. This bimodal behavior also depends on the germanium content as high Ge-content further decreases <b>UTL</b> hydrolytic stability by opening up yet another low-energy disassembly pathway at high water loading. Overall, we discovered, verified and explained the mechanisms of <b>UTL</b> disassembly and its factors. These findings will likely be generalized to other ADORable germanosilicate zeolites and help to find the optimal protocol for the synthesis of new zeolites.