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B/N 共掺杂纳米碳在苯甲醇选择性氧化中活性位的鉴定。

Identification of active sites of B/N co-doped nanocarbons in selective oxidation of benzyl alcohol.

机构信息

Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials, College of Chemistry, Fuzhou University, Fuzhou 350116, China.

School of Pharmaceutical and Materials Engineering, Taizhou University, Taizhou 318000, Zhejiang Province, China.

出版信息

J Colloid Interface Sci. 2022 Feb 15;608(Pt 3):2801-2808. doi: 10.1016/j.jcis.2021.11.001. Epub 2021 Nov 4.

Abstract

Developing highly active and stable nanocarbon catalysts for selective oxidation reactions has attracted much attention due to their potential as an alternative to traditional metal-based or noble metal catalysts. However, the nature of active sites and the reaction mechanism of nanocarbon catalysts for oxidation reactions still remains largely unknown, which hinders the rational design and development of highly efficient carbon-based catalysts. Here we report a facile strategy for the synthesis of boron and nitrogen co-doped carbon nanosheet material (BNC), which exhibits excellent catalytic activity with 91% conversion and 99% selectivity in selective oxidation of benzyl alcohol into benzaldehyde, superior to those of traditional carbon materials (oxidized carbon nanotubes, graphites and commercial nanocarbons). Structural characterizations and kinetic measurements are studied to clarify the active site, in which phenolic hydroxyl on BNC is responsible for the production of benzaldehyde. Meanwhile, we put forward a possible reaction mechanism and point out the key factors in determining the reactivity for this reaction. Therefore, the present work provides new insight into structure-function relationships, paving the way for the development of highly efficient nanocarbon catalysts.

摘要

由于纳米碳催化剂在选择性氧化反应中作为传统金属基或贵金属催化剂的替代品具有很大的潜力,因此开发高活性和稳定的纳米碳催化剂引起了广泛关注。然而,纳米碳催化剂的活性位性质和氧化反应的反应机制在很大程度上仍然未知,这阻碍了高效碳基催化剂的合理设计和开发。在这里,我们报告了一种简便的硼和氮共掺杂碳纳米片材料(BNC)的合成策略,该材料在苯甲醇选择性氧化为苯甲醛的反应中表现出优异的催化活性,转化率为 91%,选择性为 99%,优于传统碳材料(氧化碳纳米管、石墨和商业纳米碳)。通过结构表征和动力学测量来阐明活性位,其中 BNC 上的酚羟基负责生成苯甲醛。同时,我们提出了一种可能的反应机制,并指出了决定反应活性的关键因素。因此,本工作为高效纳米碳催化剂的开发提供了新的结构-功能关系的见解。

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