Abstract Zeolites, a class of silica-based porous materials, have been widely employed in the chemical industry for uses such as sorption, separation, catalysis and ion exchange. Normally, the synthesis of zeolites is performed in the presence of organic templates via a trial-and-error route, which is labor-intensive and empirical. In recent years, theoretical simulation from the interaction between a zeolite structure and an organic template has been used to guide the synthesis of zeolites, which is time-saving. In this review, recent progress in the targeted synthesis of zeolites from interaction between a zeolite structure and an organic template are briefly outlined including the design of new templates for zeolite synthesis, preparation of zeolites with new composition, development of novel routes for zeolite synthesis, synthesis of intergrowth zeolites, generation of novel zeolite structures, control of zeolite morphology and modulation of aluminum distribution in zeolites. These targeted syntheses reveal that the minimum energy principle from the theoretical simulation is key for guiding zeolite crystallization. This review will be important for zeolite researchers for rationally synthesizing zeolites and effectively designing new zeolite structures.

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Targeted synthesis of zeolites from calculated interaction between zeolite structure and organic template

Zeolites, a class of silica-based porous materials, have been widely employed in the chemical industry for uses such as sorption, separation, catalysis and ion exchange. Normally, the synthesis of zeolites is performed in the presence of organic templates via a trial-and-error route, which is labor-intensive and empirical. In recent years, theoretical simulation from the interaction between a zeolite structure and an organic template has been used to guide the synthesis of zeolites, which is time-saving. In this review, recent progress in the targeted synthesis of zeolites from interaction between a zeolite structure and an organic template are briefly outlined including the design of new templates for zeolite synthesis, preparation of zeolites with new composition, development of novel routes for zeolite synthesis, synthesis of intergrowth zeolites, generation of novel zeolite structures, control of zeolite morphology and modulation of aluminum distribution in zeolites. These targeted syntheses reveal that the minimum energy principle from the theoretical simulation is key for guiding zeolite crystallization. This review will be important for zeolite researchers for rationally synthesizing zeolites and effectively designing new zeolite structures. 

OUP accepted manuscript

Zeolites are typically a class of crystalline microporous aluminosilicates that are constructed by SiO4 and AlO4 tetrahedra. Because of their unique porous structures, strong Brönsted acidity, molecular-level shape selectivity, exchangeable cations, and high thermal/hydrothermal stability, zeolites are widely used as catalysts, adsorbents, and ion-exchangers in industry. The activity, selectivity, and stability/durability of zeolites in applications are closely related to their Si/Al ratios and Al distributions in the framework. In this review, we discussed the basic principles and the state-of-the-art methodologies for regulating the Si/Al ratios and Al distributions of zeolites, including seed-assisted recipe modification, interzeolite transformation, fluoride media, and usage of organic structure-directing agents (OSDAs), etc. The conventional and newly developed characterization methods for determining the Si/Al ratios and Al distributions were summarized, which include X-ray fluorescence spectroscopy (XRF), solid state 29Si/27Al magic-angle-spinning nuclear magnetic resonance spectroscopy (29Si/27Al MAS NMR), Fourier-transform infrared spectroscopy (FT-IR), etc. The impact of Si/Al ratios and Al distributions on the catalysis, adsorption/separation, and ion-exchange performance of zeolites were subsequently demonstrated. Finally, we presented a perspective on the precise control of the Si/Al ratios and Al distributions of zeolites and the corresponding challenges.

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Regulation of the Si/Al ratios and Al distributions of zeolites and their impact on properties

Abstract (1S,2S)‐N‐methyl‐pseudoephedrine (MPS) was used as organic structure‐directing agent (OSDA) for the synthesis of Mg‐doped nanoporous aluminophosphates. This molecule displays a particular conformational behavior, where the presence of H‐bond donor and acceptor groups provide a rigid conformational space with one asymmetric conformation preferentially occurring. MPS drives the crystallization of Mg‐containing AFI materials. Characterization of these materials shows that the OSDA incorporate as protonated species, arranged as head‐to‐tail monomers. Combination of three‐dimensional electron diffraction with high‐resolution synchrotron powder X‐ray diffraction allowed to locate both the Mg and the organic species. Interestingly, results showed that the spatial incorporation of Mg is driven by the hydroxyl groups of the organic cation through the development of H‐bonds with negatively‐charged MgO4 tetrahedra. This work demonstrates that H‐bond forming groups can be used to drive the spatial incorporation of low‐valent dopants within zeolitic frameworks, a highly desired aim in order to control their catalytic activity and selectivity.

Driving the Active Site Incorporation in Zeolitic Materials via the Organic Structure‐Directing Agent Through Development of H‐Bonds with Hydroxyl Groups

MSE-type zeolites synthesized by different organic structure-directing agents (OSDAs), UZM-35 and MCM-68, were prepared. The location of Brønsted acid sites derived from the framework Al atoms and acidic properties were investigated based on 27Al MQMAS NMR and in situ IR techniques combined with the evaluation of the catalytic activity. We have successfully found a significant difference in the location of Brønsted acid sites in the MSE-type framework; 61 and 33% of acid sites were located at the 12-ring channel for MCM-68 and UZM-35, respectively. The differences in the location of the acid sites yielded their unique catalytic activities for the hydrocarbon cracking reactions, indicating that a well-chosen type of OSDAs for the synthesis is one of the possibilities for controlling the distribution of the framework Al atoms in the MSE-type framework.

Clarification of acid site location in MSE-type zeolites by spectroscopic approaches combined with catalytic activity: comparison between UZM-35 and MCM-68.

Organic and inorganic structure-directing agents (SDAs) impact Al distributions in zeolite, but the insights into how SDAs manipulate Al distribution have not been elucidated yet. Herein, the roles of different SDAs such as cyclohexylamine (CHA), hexamethylenimine (HMI), and Na+ in selective Al substitution of MCM-49 zeolite are investigated comprehensively by multinuclear solid-state NMR. The results demonstrate that MCM-49 synthesized with HMI shows relatively more T6 and T7 Al, while more T2 Al is observed using CHA. The formation of T2 Al in both MCM-49(HMI) and MCM-49(CHA) is derived from Na+, while protonated HMIs show bias in incorporation of T6 and T7 Al. Most HMIs are occluded in protonated status, and about half of CHAs are occluded in nonprotonated status. The close spatial proximity between nonprotonated CHAs and Na+ synergistically promotes the formation of zeolite structure, leading to more Na+ ions occluded in the zeolite channel with preferential T2 Al substitution.

Zhili Wang

Papers

The Role of Organic and Inorganic Structure-Directing Agents in Selective Al Substitution of Zeolite.