Accelerated selective oxidation of benzyl alcohol to benzaldehyde via a self-catalyzed Pickering emulsion microreactor
Dan, Hongbing; Zhao, Han; Gao, Yue; Zhang, Baiyu; Xu, Xing; Yue, Qinyan; Leiviskä, Tiina; Jin, Bo; Chen, Bing; Gao, Baoyu (2024-08-28)
Avaa tiedosto
Sisältö avataan julkiseksi: 28.08.2025
Royal society of chemistry
28.08.2024
Dan, H., Zhao, H., Gao, Y., Zhang, B., Xu, X., Yue, Q., Leiviskä, T., Jin, B., Chen, B., & Gao, B. (2024). Accelerated selective oxidation of benzyl alcohol to benzaldehyde via a self-catalyzed Pickering emulsion microreactor. Journal of Materials Chemistry A, 12(37), 25381–25392. https://doi.org/10.1039/D4TA04195J
https://rightsstatements.org/vocab/InC/1.0/
© The Royal Society of Chemistry 2024
https://rightsstatements.org/vocab/InC/1.0/
© The Royal Society of Chemistry 2024
https://rightsstatements.org/vocab/InC/1.0/
Julkaisun pysyvä osoite on
https://urn.fi/URN:NBN:fi:oulu-202409125808
https://urn.fi/URN:NBN:fi:oulu-202409125808
Tiivistelmä
Abstract
Selective oxidation of alcohols to aldehyde or ketone is a fundamental reaction in organic synthesis. Herein, a self-catalyzed Pickering emulsion microreactor (PEM) was designed for the selective oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) using peroxymonosulfate (PMS) as an oxidant. Featuring inherent pyridinic N and pyridine N-oxide species, Enteromorpha prolifera-derived biochar displayed particular super-amphiphilicity, able to serve as an emulsifier and catalyst simultaneously in the PMS-based PEM (PPEM) system. The results showed that, without extra additives, the PPEM system could 100% selectively oxidize 2.88 mM of BzOH to BzH (yield: 90.4%) within 30 min at room temperature. After systematic and theoretical studies, we found that radical (O2˙−) and non-radical (1O2 and mediated electron transfer) oxidation routes were responsible for the selective BzOH oxidation to BzH, where the reaction energy barrier for the oxidation of BzOH by 1O2 (18.0 kcal mol−1) is lower compared to that of O2˙− (25.8 kcal mol−1). Overall, the rationally fabricated biochar with special surface wettability and catalytic activity offers a novel emulsion self-catalysis route to achieve the selective oxidation of alcohol.
Selective oxidation of alcohols to aldehyde or ketone is a fundamental reaction in organic synthesis. Herein, a self-catalyzed Pickering emulsion microreactor (PEM) was designed for the selective oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) using peroxymonosulfate (PMS) as an oxidant. Featuring inherent pyridinic N and pyridine N-oxide species, Enteromorpha prolifera-derived biochar displayed particular super-amphiphilicity, able to serve as an emulsifier and catalyst simultaneously in the PMS-based PEM (PPEM) system. The results showed that, without extra additives, the PPEM system could 100% selectively oxidize 2.88 mM of BzOH to BzH (yield: 90.4%) within 30 min at room temperature. After systematic and theoretical studies, we found that radical (O2˙−) and non-radical (1O2 and mediated electron transfer) oxidation routes were responsible for the selective BzOH oxidation to BzH, where the reaction energy barrier for the oxidation of BzOH by 1O2 (18.0 kcal mol−1) is lower compared to that of O2˙− (25.8 kcal mol−1). Overall, the rationally fabricated biochar with special surface wettability and catalytic activity offers a novel emulsion self-catalysis route to achieve the selective oxidation of alcohol.
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