Understanding of the Oxidation Behavior of Benzyl Alcohol by Peroxymonosulfate via Carbon Nanotubes Activation,ACS Catalysis

当前位置： X-MOL 学术 › ACS Catal. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Understanding of the Oxidation Behavior of Benzyl Alcohol by Peroxymonosulfate via Carbon Nanotubes Activation
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-02-28 , DOI: 10.1021/acscatal.9b05273
Jiaquan Li ₁ , Mengting Li ₂ , Hongqi Sun ₃ , Zhimin Ao ₂ , Shaobin Wang ₄ , Shaomin Liu _{1,

5}

Affiliation

Selective oxidation of benzyl alcohol (BzOH) into benzaldehyde (BzH) is very important in synthetic chemistry. Peroxymonosulfate (PMS) is a cheap, stable, and soluble solid oxidant, holding promise for organic oxidation reactions. Herein, we report the catalytic PMS activation via carbon nanotubes (CNTs) for the selective oxidation of BzOH under mild conditions without other additives. A remarkable promotion of BzH yield with a selectivity over 80% was achieved on modified CNTs, i.e., O-CNTs via the radical oxidation process, and the oxygen functionalities for catalysis were comprehensively investigated by experimental study and theoretical exploration. To understand the different surface oxygen species on CNTs for the activation of PMS, density functional theory (DFT) calculations were performed to investigate the adsorption behavior of PMS on various CNTs. The electrophilic oxygen was identified as the electron captor to activate PMS by O–O bond cleavage to form SO₅^•– and SO₄^•– radicals. The nucleophilic carbonyl groups can also induce a redox cycle to generate ^•OH and SO₄^•– radicals, but phenolic hydroxyl groups impede the radical process with antioxidative functionality. The carbocatalysis-assisted PMS activation may provide a cheap process for the selective oxidation of alcohols into aldehydes or ketones. The insight achieved from this fundamental study may be further applied to other organic syntheses via selective oxidation.

中文翻译：

通过碳纳米管活化了解过氧一硫酸盐对苄醇的氧化行为

在合成化学中，将苄醇（BzOH）选择性氧化为苯甲醛（BzH）非常重要。过氧一硫酸盐（PMS）是一种廉价，稳定且可溶的固体氧化剂，有望用于有机氧化反应。在本文中，我们报告了在不添加其他添加剂的情况下，通过碳纳米管（CNT）催化PMS活化以选择性氧化BzOH的过程。通过自由基氧化工艺，在改性的CNTs，即O-CNTs上，选择性显着提高了BzH的收率，选择性达到80％以上，并通过实验研究和理论探索对催化剂的氧官能度进行了全面研究。要了解CNT上用于激活PMS的不同表面氧种类，进行了密度泛函理论（DFT）计算，以研究PMS在各种CNT上的吸附行为。亲电子氧被认为是通过O-O键裂解形成SO激活PMS的电子俘获剂₅^•–和SO ₄^•–自由基。亲核羰基还可以诱导氧化还原循环，从而产生^• OH和SO ₄^•-自由基，但是酚羟基具有抗氧化功能，可阻止自由基过程。碳催化辅助的PMS活化可以为将醇选择性氧化为醛或酮提供廉价的过程。从基础研究中获得的见识可以通过选择性氧化进一步应用于其他有机合成。

更新日期：2020-02-28

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南