A stable zeolite with atomically ordered and interconnected mesopore channel

Zeolites are crystalline microporous materials constructed by corner-sharing tetrahedra (SiO<sub>4</sub> and AlO<sub>4</sub>), with many industrial applications as ion exchangers, adsorbents and heterogeneous catalysts<sup>1-4</sup>. However, the presence of micropores impedes the use of zeolites in areas dealing with bulky substrates. Introducing extrinsic mesopores, that is, intercrystal/intracrystal mesopores, in zeolites is a solution to overcome the diffusion barrier<sup>5-8</sup>. Still, those extrinsic mesopores are generally disordered and non-uniform; moreover, acidity and crystallinity are always, to some extent, impaired<sup>9</sup>. Thus, synthesizing thermally stable zeolites with intrinsic mesopores that are of uniform size and crystallographically connected with micropores, denoted here as intrinsic mesoporous zeolite, is highly desired but still not achieved. Here we report ZMQ-1 (Zeolitic Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, no. 1), an aluminosilicate zeolite with an intersecting intrinsic meso-microporous channel system delimited by 28 × 10 × 10-rings, in which the 28-ring has a free diameter of 22.76 Å × 11.83 Å, which reaches the mesopore domain. ZMQ-1 has high thermal and hydrothermal stability with tunable framework Si/Al molar ratios. ZMQ-1 is the first aluminosilicate zeolite with an intrinsic meso-microporous channel system. The Brønsted acidity of ZMQ-1 imparts high activity and unique selectivity in the catalytic cracking of heavy oil. The position of the organic structure-directing agent (OSDA) used for ZMQ-1 synthesis was determined from three-dimensional electron diffraction (3D ED) data, which shows the unique structure-directing role of the OSDA in the formation of the intrinsic meso-microporous zeolite. This provides an incentive for preparing other stable mesopore-containing zeolites.

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Publication Details

Journal
Nature
Published
2024-12-11
DOI
https://doi.org/10.1038/s41586-024-08206-1
Citations
69
Primary Topic
Zeolite Catalysis and Synthesis
Type
article
Field-Weighted Citation Impact
10.93

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article

A stable zeolite with atomically ordered and interconnected mesopore channel

Valentin Valtchev, Xiaodong Zou, Xiaobo Yang, Tom Willhammar et al.
69 citations
Nature
Zeolite Catalysis and Synthesis
10.93
article

A stable zeolite with atomically ordered and interconnected mesopore channel

Valentin Valtchev, Xiaodong Zou, Xiaobo Yang, Tom Willhammar, Svetlana Mintova, Qiaolin Lang, Jung Cho, Hongyi Xu, Zhaopeng Liu, Mohammad Fahda, Eddy Dib, Peng Lü, Zhengxing Qin, Rémy Guillet‐Nicolas, Bo Wang, Yiqing Sun, Jiaoyan Xu, Haijun Yu
article en
69 citations

Abstract

Zeolites are crystalline microporous materials constructed by corner-sharing tetrahedra (SiO<sub>4</sub> and AlO<sub>4</sub>), with many industrial applications as ion exchangers, adsorbents and heterogeneous catalysts<sup>1-4</sup>. However, the presence of micropores impedes the use of zeolites in areas dealing with bulky substrates. Introducing extrinsic mesopores, that is, intercrystal/intracrystal mesopores, in zeolites is a solution to overcome the diffusion barrier<sup>5-8</sup>. Still, those extrinsic mesopores are generally disordered and non-uniform; moreover, acidity and crystallinity are always, to some extent, impaired<sup>9</sup>. Thus, synthesizing thermally stable zeolites with intrinsic mesopores that are of uniform size and crystallographically connected with micropores, denoted here as intrinsic mesoporous zeolite, is highly desired but still not achieved. Here we report ZMQ-1 (Zeolitic Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, no. 1), an aluminosilicate zeolite with an intersecting intrinsic meso-microporous channel system delimited by 28 × 10 × 10-rings, in which the 28-ring has a free diameter of 22.76 Å × 11.83 Å, which reaches the mesopore domain. ZMQ-1 has high thermal and hydrothermal stability with tunable framework Si/Al molar ratios. ZMQ-1 is the first aluminosilicate zeolite with an intrinsic meso-microporous channel system. The Brønsted acidity of ZMQ-1 imparts high activity and unique selectivity in the catalytic cracking of heavy oil. The position of the organic structure-directing agent (OSDA) used for ZMQ-1 synthesis was determined from three-dimensional electron diffraction (3D ED) data, which shows the unique structure-directing role of the OSDA in the formation of the intrinsic meso-microporous zeolite. This provides an incentive for preparing other stable mesopore-containing zeolites.

NatureVol. 636(8042)
Qingdao University (CN), Centre National de la Recherche Scientifique (FR), Stockholm University (SE), École Nationale Supérieure d'Ingénieurs de Caen (FR), Peking University (CN), Ruijin Hospital (CN), Normandie Université (FR), Laboratoire Catalyse et Spectrochimie (FR), Conditions Extrêmes et Matériaux Haute Température et Irradiation (FR), Shanghai Institute of Hematology (CN), Qingdao Institute of Bioenergy and Bioprocess Technology (CN), China University of Petroleum, East China (CN), Ocean University of China (CN), Université de Caen Normandie (FR)
National Natural Science Foundation of China, Knut och Alice Wallenbergs Stiftelse, Vetenskapsrådet, Stockholms Universitet, Science for Life Laboratory
Openalex Percentile: Top 1%
Zeolite Catalysis and Synthesis
10.93
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