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Silicoaluminophosphate zeolite (SAPO‐34) has been attracting increasing attention due to its excellent form selection and controllability in the chemical industry, as well as being one of the best industrial catalysts for methanol‐to‐olefin (MTO) reaction conversion. However, as a microporous molecular sieve, SAPO‐34 easily generates carbon deposition and rapidly becomes inactivated. Therefore, it is necessary to reduce the crystal size of the zeolite or to introduce secondary macropores into the zeolite crystal to form a hierarchical structure in order to improve the catalytic effect. In this review, the synthesis methods of conventional SAPO‐34 molecular sieves, hierarchical SAPO‐34 molecular sieves and nanosized SAPO‐34 molecular sieves are introduced, and the properties of the synthesized SAPO‐34 molecular sieves are described, including the phase, morphology, pore structure, acid source, and catalytic performance, in particular with respect to the synthesis of hierarchical SAPO‐34 molecular sieves. We hope that the review can provide guidance to the preparation of the SAPO‐34 catalysts, and stimulate the future development of high‐performance hierarchical SAPO‐34 catalysts to meet the growing demands of the material and chemical industries.

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The methanol‐to‐olefins reaction has received considerable interest owing to its importance in converting abundant resources, such as coal, natural gas and biomass, to widely demanded light olefins. SAPO‐34, with a CHA topological structure, has high methanol conversion and excellent selectivity for light olefins. For more details on the efficient synthesis and the use of the SAPO‐34 molecular sieves, see the Review by X. Wu et al. (DOI: 10.1002/chem.202102787).

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