Issue 46, 2023

Spontaneous generation of singlet oxygen on microemulsion-derived manganese oxides with rich oxygen vacancies for efficient aerobic oxidation

Abstract

Developing innovative catalysts for efficiently activating O2 into singlet oxygen (1O2) is a cutting-edge field with the potential to revolutionize green chemical synthesis. Despite its potential, practical implementation remains a significant challenge. In this study, we design a series of nitrogen (N)-doped manganese oxides (Ny-MnO2, where y represents the molar amount of the N precursor used) nanocatalysts using compartmentalized-microemulsion crystallization followed by post-calcination. These nanocatalysts demonstrate the remarkable ability to directly produce 1O2 at room temperature without the external fields. By strategically incorporating defect engineering and interstitial N, the concentration of surface oxygen atoms (Os) in the vicinity of oxygen vacancy (Ov) reaches 51.1% for the N55-MnO2 nanocatalyst. This feature allows the nanocatalyst to expose a substantial number of Ov and interstitial N sites on the surface of N55-MnO2, facilitating effective chemisorption and activation of O2. Verified through electron paramagnetic resonance spectroscopy and reactive oxygen species trapping experiments, the spontaneous generation of 1O2, even in the absence of light, underscores its crucial role in aerobic oxidation. Density functional theory calculations reveal that an increased Ov content and N doping significantly reduce the adsorption energy, thereby promoting chemisorption and excitation of O2. Consequently, the optimized N55-MnO2 nanocatalyst enables room-temperature aerobic oxidation of alcohols with a yield surpassing 99%, representing a 6.7-fold activity enhancement compared to ε-MnO2 without N-doping. Furthermore, N55-MnO2 demonstrates exceptional recyclability for the aerobic oxidative conversion of benzyl alcohol over ten cycles. This study introduces an approach to spontaneously activate O2 for the green synthesis of fine chemicals.

Graphical abstract: Spontaneous generation of singlet oxygen on microemulsion-derived manganese oxides with rich oxygen vacancies for efficient aerobic oxidation

Supplementary files

Article information

Article type
Edge Article
Submitted
23 avq 2023
Accepted
09 okt 2023
First published
12 okt 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 13402-13409

Spontaneous generation of singlet oxygen on microemulsion-derived manganese oxides with rich oxygen vacancies for efficient aerobic oxidation

J. Tang, J. Chen, Z. Zhang, Q. Ma, X. Hu, P. Li, Z. Liu, P. Cui, C. Wan, Q. Ke, L. Fu, J. Kim, T. Hamada, Y. Kang and Y. Yamauchi, Chem. Sci., 2023, 14, 13402 DOI: 10.1039/D3SC04418A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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