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 stems from the rapid decrease in d-spacing upon hydrolysis (disassembly). Nevertheless, we have artificially increased the d-spacing of layered IPC-1P by intercalating organic species. Furthermore, we have reconstructed double four rings (D4R) between layers, thus transforming IPC-1P back into the parent UTL zeolite. This reconstruction has provided not only germanosilicate but also a new, high-silica UTL zeolite (Si/Ge = 481). Therefore, our "reverse ADOR" opens up new synthetic routes towards promising extra-large-pore zeolite-based materials with new chemical compositions.

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• Journal Article MeSH

The ADOR (Assembly-Disassembly-Organisation-Reassembly) process for zeolites has been shown to produce a number of previously unknown frameworks inaccessible through conventional synthesis methods. Here, we present successful mechanochemically assisted hydrolysis of germanosilicate zeolite UTL leading to ADOR products under mild conditions, low amounts of solvent and in short reaction times. The expansion of zeolite synthesis into the realm of mechanochemistry opens up feasible pathways regarding the production of these materials, especially for industrial purposes, as well as an exciting application for economical enrichment of materials with the low natural abundance NMR-active isotope of oxygen, 17O. The results from mechanochemically assisted hydrolysis differ from those seen in the traditional ADOR approach: differences that can be attributed to a change in solvent availability.

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• Journal Article MeSH

The hydrolysis (disassembly, D) and rearrangement (organization, O) steps of the assembly-disassembly-organization-reassembly (ADOR) process for the synthesis of zeolites have been studied. Germanium-rich UTL was subjected to hydrolysis conditions in water to understand the effects of temperature (100, 92, 85, 81, 77, and 70 °C). Samples were taken periodically over an 8-37 h period, and each sample was analyzed by powder X-ray diffraction. The results show that the hydrolysis step is solely dependent on the presence of liquid water, whereas the rearrangement is dependent on the temperature of the system. The kinetics have been investigated using the Avrami-Erofeev model. With increasing temperature, an increase in the rate of reaction for the rearrangement step was observed, and the Arrhenius equation was used to ascertain an apparent activation energy for the rearrangement from the kinetic product of the disassembly (IPC-1P) to the thermodynamic product of the rearrangement (IPC-2P). From this information, a mechanism for this transformation can be postulated.

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• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH

The assembly-disassembly-organization-reassembly (ADOR) mechanism is a recent method for preparing inorganic framework materials and, in particular, zeolites. This flexible approach has enabled the synthesis of isoreticular families of zeolites with unprecedented continuous control over porosity, and the design and preparation of materials that would have been difficult-or even impossible-to obtain using traditional hydrothermal techniques. Applying the ADOR process to a parent zeolite with the UTL framework topology, for example, has led to six previously unknown zeolites (named IPC-n, where n = 2, 4, 6, 7, 9 and 10). To realize the full potential of the ADOR method, however, a further understanding of the complex mechanism at play is needed. Here, we probe the disassembly, organization and reassembly steps of the ADOR process through a combination of in situ solid-state NMR spectroscopy and powder X-ray diffraction experiments. We further use the insight gained to explain the formation of the unusual structure of zeolite IPC-6.

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• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH

The assembly-disassembly-organization-reassembly (ADOR) process has been used to disassemble a parent zeolite with the UOV structure type and then reassemble the resulting layers into a novel structure, IPC-12. The structure of the material has previously been predicted computationally and confirmed in our experiments using X-ray diffraction and atomic resolution STEM-HAADF electron microscopy. This is the first successful application of the ADOR process to a material with porous layers.

• Keywords
• ADOR, germanosilicates, isoreticular materials, structure rearrangement, zeolites,
• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH

Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum--why have so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such 'unfeasible' zeolites, IPC-9 and IPC-10, through the assembly-disassembly-organization-reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications.

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• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH

Weakness in a material, especially when challenged by chemical, mechanical or physical stimuli, is often viewed as something extremely negative. There are countless examples in which interesting-looking materials have been dismissed as being too unstable for an application. But instability with respect to a stimulus is not always a negative point. In this Perspective we highlight situations where weakness in a material can be used as a synthetic tool to prepare materials that, at present, are difficult or even impossible to prepare using traditional synthetic approaches. To emphasize the concept, we will draw upon examples in the field of nanoporous materials, concentrating on metal-organic frameworks and zeolites, but the general concepts are likely to be applicable across a wide range of materials chemistry. In zeolite chemistry, there is a particular problem with accessing hypothetical structures that this approach may solve.

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• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH

Hydrolysis of germanosilicate zeolites with the IWW structure shows two different outcomes depending on the composition of the starting materials. Ge-rich IWW (Si/Ge=3.1) is disassembled into a layered material (IPC-5P), which can be reassembled into an almost pure silica IWW on treatment with diethoxydimethylsilane. Ge-poor IWW (Si/Ge=6.4) is not completely disassembled on hydrolysis, but retains some 3D connectivity. This structure can be reassembled into IWW by incorporation of Al to fill the defects left when the Ge is removed.

• Keywords
• ADOR, IWW, germanosilicate, solid-state transformation, zeolites,
• Publication type
• Journal Article MeSH

The properties of zeolites, and thus their suitability for different applications, are intimately connected with their structures. Synthesizing specific architectures is therefore important, but has remained challenging. Here we report a top-down strategy that involves the disassembly of a parent zeolite, UTL, and its reassembly into two zeolites with targeted topologies, IPC-2 and IPC-4. The three zeolites are closely related as they adopt the same layered structure, and they differ only in how the layers are connected. Choosing different linkers gives rise to different pore sizes, enabling the synthesis of materials with predetermined pore architectures. The structures of the resulting zeolites were characterized by interpreting the X-ray powder-diffraction patterns through models using computational methods; IPC-2 exhibits orthogonal 12- and ten-ring channels, and IPC-4 is a more complex zeolite that comprises orthogonal ten- and eight-ring channels. We describe how this method enables the preparation of functional materials and discuss its potential for targeting other new zeolites.

• MeSH
• Magnetic Resonance Spectroscopy MeSH
• Models, Molecular MeSH
• Powder Diffraction MeSH
• Zeolites chemistry   MeSH
• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH
• Names of Substances
• Zeolites MeSH