Dynamic Lewis and Brønsted Synergistic Mechanism in Ga-Modified Hβ Molecular Sieves: Selective Synthesis of 2-Ethylanthraquinone Driven by Electron Redistribution

The precise regulation of multistep reaction paths in the synthesis of 2-ethylanthraquinone, with lower yields due to contradictions in the stability of intermediates and compatibility of active sites, poses a great challenge to industrial production. In this study, an electron redistribution strategy is proposed: By anchoring the active metal gallium to the Hβ molecular sieve framework, a Lewis and Brønsted acid pair that can dynamically adapt the reaction path is constructed. Based on the Friedel–Crafts acylation reaction, it was revealed that the Ga3+ center undergoes a valence transition during the catalytic process, which synergizes with the Brønsted acidic site (Si–OH-Al) to regulate the adsorption configuration of the intermediates, and improves the catalytic efficiency of the modified Hβ molecular sieves. Compared to the conventional sulfuric acid method (E = 5.2), a yield of 89.3% was achieved with an E coefficient of 0.8, a reduction of 85%. By optimizing the reaction temperature to 250 °C (300 °C for the acid-catalyzed method), energy consumption was reduced by 37%, while sulfonation waste was reduced by 1.6 tons per ton of product. The hierarchical pore structure of Ga–Hβ enhanced molecular diffusion efficiency, reducing activation energy by 35% (40.07 kJ·mol–1 for Ga–Hβ vs 62.11 kJ·mol–1 for H2SO4) and enabling four stable regeneration cycles with 80% activity retention. It provides a universal theoretical framework for space-time regulation of multistep catalytic networks in complex organic synthesis and provides a new direction for industrial catalytic synthesis of 2-ethylanthraquinones.

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Journal
ACS Sustainable Chemistry & Engineering
Published
2025-05-30
DOI
https://doi.org/10.1021/acssuschemeng.5c01903
Primary Topic
Advanced Chemical Physics Studies
Type
article
Field-Weighted Citation Impact
0.00

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article

Dynamic Lewis and Brønsted Synergistic Mechanism in Ga-Modified Hβ Molecular Sieves: Selective Synthesis of 2-Ethylanthraquinone Driven by Electron Redistribution

Qilong Zhao, Yao Nie, Huihui Wang, Mingming Han et al.
ACS Sustainable Chemistry & Engineering
Advanced Chemical Physics Studies
article

Dynamic Lewis and Brønsted Synergistic Mechanism in Ga-Modified Hβ Molecular Sieves: Selective Synthesis of 2-Ethylanthraquinone Driven by Electron Redistribution

Qilong Zhao, Yao Nie, Huihui Wang, Mingming Han, Yue Liu, Shiwei Liu, Miao Yu, Jialuo Yin, Sai Geng, Pengpeng Wen, Jingyi Lao, Anyang Shi
article en

Abstract

The precise regulation of multistep reaction paths in the synthesis of 2-ethylanthraquinone, with lower yields due to contradictions in the stability of intermediates and compatibility of active sites, poses a great challenge to industrial production. In this study, an electron redistribution strategy is proposed: By anchoring the active metal gallium to the Hβ molecular sieve framework, a Lewis and Brønsted acid pair that can dynamically adapt the reaction path is constructed. Based on the Friedel–Crafts acylation reaction, it was revealed that the Ga3+ center undergoes a valence transition during the catalytic process, which synergizes with the Brønsted acidic site (Si–OH-Al) to regulate the adsorption configuration of the intermediates, and improves the catalytic efficiency of the modified Hβ molecular sieves. Compared to the conventional sulfuric acid method (E = 5.2), a yield of 89.3% was achieved with an E coefficient of 0.8, a reduction of 85%. By optimizing the reaction temperature to 250 °C (300 °C for the acid-catalyzed method), energy consumption was reduced by 37%, while sulfonation waste was reduced by 1.6 tons per ton of product. The hierarchical pore structure of Ga–Hβ enhanced molecular diffusion efficiency, reducing activation energy by 35% (40.07 kJ·mol–1 for Ga–Hβ vs 62.11 kJ·mol–1 for H2SO4) and enabling four stable regeneration cycles with 80% activity retention. It provides a universal theoretical framework for space-time regulation of multistep catalytic networks in complex organic synthesis and provides a new direction for industrial catalytic synthesis of 2-ethylanthraquinones.

ACS Sustainable Chemistry & EngineeringVol. 13(22)
Qingdao University of Science and Technology (CN)
National Natural Science Foundation of China, China Postdoctoral Science Foundation, Natural Science Foundation of Shandong Province, Postdoctoral Innovation Project of Shandong Province, National College Students Innovation and Entrepreneurship Training Program
Zero hunger
Openalex Percentile: Top 91%
Advanced Chemical Physics Studies
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