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Accelerated selective oxidation of benzyl alcohol to benzaldehyde via a self-catalyzed Pickering emulsion microreactor
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2024-08-28 , DOI: 10.1039/d4ta04195j Hongbing Dan 1, 2 , Han Zhao 1 , Yue Gao 1 , Baiyu Zhang 2 , Xing Xu 1 , Qinyan Yue 1 , Tiina Leiviskä 3 , Bo Jin 4 , Bing Chen 2 , Baoyu Gao 1
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2024-08-28 , DOI: 10.1039/d4ta04195j Hongbing Dan 1, 2 , Han Zhao 1 , Yue Gao 1 , Baiyu Zhang 2 , Xing Xu 1 , Qinyan Yue 1 , Tiina Leiviskä 3 , Bo Jin 4 , Bing Chen 2 , Baoyu Gao 1
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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.
中文翻译:
自催化Pickering乳液微反应器加速苯甲醇选择性氧化为苯甲醛
醇选择性氧化为醛或酮是有机合成中的基本反应。在此,设计了一种自催化Pickering乳液微反应器(PEM),用于使用过一硫酸盐(PMS)作为氧化剂将苯甲醇(BzOH)选择性氧化为苯甲醛(BzH)。浒苔衍生的生物炭具有固有的吡啶N和吡啶N-氧化物物种,表现出特殊的超两亲性,能够在基于PMS的质子交换膜(PPEM)系统中同时充当乳化剂和催化剂。结果表明,在没有额外添加剂的情况下,PPEM系统可以在室温下30分钟内100%选择性地将2.88 mM BzOH氧化为BzH(产率:90.4%)。经过系统和理论研究,我们发现自由基(O 2 ˙ - )和非自由基( 1 O 2和介导的电子转移)氧化途径导致BzOH选择性氧化为BzH,其中氧化的反应能垒1 O 2的BzOH (18.0 kcal mol -1 ) 比O 2 ˙ - (25.8 kcal mol -1 ) 的低。总的来说,合理制备的生物炭具有特殊的表面润湿性和催化活性,为实现醇的选择性氧化提供了一种新颖的乳液自催化途径。
更新日期:2024-09-02
中文翻译:
![](https://scdn.x-mol.com/jcss/images/paperTranslation.png)
自催化Pickering乳液微反应器加速苯甲醇选择性氧化为苯甲醛
醇选择性氧化为醛或酮是有机合成中的基本反应。在此,设计了一种自催化Pickering乳液微反应器(PEM),用于使用过一硫酸盐(PMS)作为氧化剂将苯甲醇(BzOH)选择性氧化为苯甲醛(BzH)。浒苔衍生的生物炭具有固有的吡啶N和吡啶N-氧化物物种,表现出特殊的超两亲性,能够在基于PMS的质子交换膜(PPEM)系统中同时充当乳化剂和催化剂。结果表明,在没有额外添加剂的情况下,PPEM系统可以在室温下30分钟内100%选择性地将2.88 mM BzOH氧化为BzH(产率:90.4%)。经过系统和理论研究,我们发现自由基(O 2 ˙ - )和非自由基( 1 O 2和介导的电子转移)氧化途径导致BzOH选择性氧化为BzH,其中氧化的反应能垒1 O 2的BzOH (18.0 kcal mol -1 ) 比O 2 ˙ - (25.8 kcal mol -1 ) 的低。总的来说,合理制备的生物炭具有特殊的表面润湿性和催化活性,为实现醇的选择性氧化提供了一种新颖的乳液自催化途径。