M−N3 Configuration on Boron Nitride Boosts Singlet Oxygen Generation via Peroxymonosulfate Activation for Selective Oxidation

• Published in: Angewandte Chemie International Edition 2024-06, Vol.63 (26), p.e202402669-n/a
• Main Authors: Zhen, Jianzheng, Sun, Jiahao, Xu, Xiangwei, Wu, Zenglong, Song, Wenkai, Ying, Yunzhan, Liang, Shikun, Miao, Lingshan, Cao, Jiazhen, Lv, Weiyang, Song, Changsheng, Yao, Yuyuan, Xing, Mingyang
• Format: Article
• Language: English
• Subjects: Alcohols; Aldehydes; Boron; Boron nitride; Catalysts; Catalytic activity; Chemical synthesis; Controllability; Fenton-like reaction; Membrane filtration; Organic matter; Oxidation; selective oxidation; Selectivity; single-atom catalysts; Singlet oxygen
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202402669

Singlet oxygen (1O2) is an essential reactive species responsible for selective oxidation of organic matter, especially in Fenton‐like processes. However, due to the great limitations in synthesizing catalysts with well‐defined active sites, the controllable production and practical application of 1O2 remain challenging. Herein, guided by theoretical simulations, a series of boron nitride‐based single‐atom catalysts (BvBN/M, M=Co, Fe, Cu, Ni and Mn) were synthesized to regulate 1O2 generation by activating peroxymonosulfate (PMS). All the fabricated BvBN/M catalysts with explicit M−N3 sites promoted the self‐decomposition of the two PMS molecules to generate 1O2 with high selectivity, where BvBN/Co possessed moderate adsorption energy and d‐band center exhibited superior catalytic activity. As an outcome, the BvBN/Co‐PMS system coupled with membrane filtration technology could continuously transform aromatic alcohols to aldehydes with nearly 100 % selectivity and conversion rate under mild conditions, suggesting the potential of this novel catalytic system for green organic synthesis. A series of boron nitride‐based single‐atom catalysts (BvBN/M, M=Co, Fe, Cu, Ni and Mn) with explicit M−N3 sites have been constructed via a vacancy control and coordination anchoring strategy, which overcome the difficulties in efficient and universal 1O2 generation by activating peroxymonosulfate (PMS), thus achieving impressive selectivity and conversion rate for the transformation of aromatic alcohols to aldehydes under mild conditions.