LSPR金属催化醇氧化制备醛类与酯类化合物的研究进展及其在日化领域的应用

doi:10.3969/j.issn.1001-1803.2022.06.013

摘要/Abstract

摘要：

醛类化合物与酯类化合物由于普遍具有杀菌、防腐以及持久香气的特点,广泛被用作日用化学品当中的添加剂使用。而醛类与酯类化合物通过醇的选择性氧化可实现低毒、绿色、无污染的合成路径。其中LSPR金属基催化剂作为醇氧化反应的优良催化剂被广泛使用。本文对LSPR金属催化醇氧化制备醛类与酯类化合物的催化机理及其催化反应的发展趋势以及在日化领域的应用进行综述,其中以Au,Ag,Cu 3种LSPR金属作活性中心,对于醇的氧化反应具有较高的催化活性,且所制备的产物醛与酯均具备选择性高的特点,使其更加有利于二者在日用化学品当中的应用。此外,从此3种金属的LSPR效应出发,对LSPR金属在光照条件下的催化机理以及光催化醇选择性氧化反应的应用进展进行综述,基于LSPR金属表面在光照下可以产生大量热电子的理论,其在醇氧化制备醛与酯的反应中,不仅可以使反应在更加温和的条件下进行,产物的选择性还可得到进一步提升。

关键词: 醛类化合物, 酯类化合物, 日用化学品, LSPR金属催化, 醇氧化, 光催化

Abstract:

Aldehydes and esters have been widely used as additives in daily chemicals due to the characteristics of sterilization, antisepsis and long-lasting aroma. The selective oxidation of alcohols to aldehydes and esters can achieve low-toxic, green and pollution-free synthetic routes. The LSPR metal catalysts are widely used as excellent catalysts for the oxidation of alcohols. Herein, the catalytic mechanism of LSPR metal-catalyzed oxidation of alcohols to aldehydes and esters are summarized, as well as the applications in the field of daily chemicals. The LSPR metals of Au, Ag and Cu are used as the active centers, which display high catalytic activity for the oxidation of alcohols, and the high selectivity to aldehydes and esters can also be obtained. In addition, the catalytic mechanism of LSPR metals under light conditions and the advances of photocatalytic selective oxidation of alcohols are reviewed based on the LSPR effects of the three metals, which can generate a large number of hot electrons on the surface of metals under light conditions. The oxidation of alcohols to aldehydes and esters can be promoted by the hot electrons. Besides, the reaction not only can be carried out under milder conditions, but also be more selective to the aldehydes and esters. In addition, the application of aldehydes and esters in daily chemical field are summarized. It is found that the aldehydes and esters prepared by the oxidation of alcohols as catalyzed by LSPR metals can achieve comparatively practical value in daily chemical field.

Key words: aldehyde, ester, daily chemical, LSPR metal catalysis, alcohol oxidation, photocatalysis

中图分类号:

TQ658

王晓宇,高晓星,王瑞义,牛宇岚. LSPR金属催化醇氧化制备醛类与酯类化合物的研究进展及其在日化领域的应用[J]. 日用化学工业, 2022, 52(6): 664-671.

Wang Xiaoyu,Gao Xiaoxing,Wang Ruiyi,Niu Yulan. Advances of LSPR metal-catalyzed oxidation of alcohols to aldehydes and esters and their application in daily chemical field[J]. China Surfactant Detergent & Cosmetics, 2022, 52(6): 664-671.

图/表 2

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催化剂	温度/K	溶剂	碱量	转化频率（TOF）/s^-1	参考文献
Au/HT	393	甲苯	/	0.22	9
Au/共聚物	308	水+氯仿	n （KOH） ∶n （醇）=1∶1	0.04	12
Au（金箔）	333	水	0.6 mol/L NaOH	2.8	14
Au（金箔）	363	甲苯	n （K₂CO₃） ∶n （醇）=1∶1	2.8	14
Au（金箔）	363	庚烷	n （K₂CO₃） ∶n （醇）=1∶1	4.4	14
Au（金箔）	333	庚烷	n （K₂CO₃） ∶n （醇）=1∶1	2.8	14
Au（金箔）	383	庚烷	n （K₂CO₃） ∶n （醇）=1∶1	5.7	14