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.
Authors
- Qilong Zhao (ORCID: https://orcid.org/0000-0001-5346-3656)
- Yao Nie (ORCID: https://orcid.org/0000-0002-8609-3345)
- Huihui Wang (ORCID: https://orcid.org/0009-0008-3871-2640)
- Mingming Han (ORCID: https://orcid.org/0000-0002-7270-474X)
- Yue Liu (ORCID: https://orcid.org/0000-0002-2663-6133)
- Shiwei Liu (ORCID: https://orcid.org/0000-0002-0396-9883)
- Miao Yu (ORCID: https://orcid.org/0000-0002-9104-4249)
- Jialuo Yin (ORCID: https://orcid.org/0009-0004-8963-8568)
- Sai Geng
- Pengpeng Wen
- Jingyi Lao
- Anyang Shi (ORCID: https://orcid.org/0009-0007-5213-0092)
Institutions
- Qingdao University of Science and Technology (CN)
Publication Details
- 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
Funders
- 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