6666-46-2Relevant articles and documents
A cobalt-substituted Keggin-Type polyoxometalate for catalysis of oxidative aromatic cracking reactions in water
Hong, Dachao,Kitagawa, Yasutaka,Kon, Yoshihiro,Shimoyama, Yoshihiro,Tamura, Satoru
, p. 8042 - 8048 (2020/12/28)
Efficient detoxification of harmful benzene rings into useful carboxylic acids in water is indispensable for achieving a clean water environment. We report herein that oxidative aromatic cracking (OAC) reactions in water were achieved using a catalytic system with a cobalt-substituted Keggin-Type polyoxometalate (Co-POM) as a catalyst, an Oxone monopersulfate compound as a sacrificial oxidant and sodium bicarbonate as an additive under mild conditions. Sodium bicarbonate plays a crucial role in the selective OAC reactions by Co-POM using ethylbenzenesulfonate as a model substrate. The reactive species was characterized to be a cobalt(iii)-oxyl species based on 31P NMR, UV-vis spectroscopic, kinetic, and theoretical analyses. The electrophilicity of the cobalt(iii)-oxyl species was demonstrated by a linear relationship with a negative slope in the Hammett plots of initial rates obtained from the OAC reactions of m-xylenesulfonate derivatives. Besides, we have verified the degradation pathway of the OAC reactions using benzene as a model substrate in the catalytic system. The degradation was initiated by an electrophilic attack of the cobalt(iii)-oxyl species on benzene to yield phenol followed by producing catechol, muconic acid, maleic/fumaric acid, tartaric acid derivatives and formic acid on the basis of 1H NMR spectroscopic analysis.
