Chitosan –NH2 derived efficient Co3O4 catalyst for styrene catalytic oxidation: Simultaneously regulating particle size and Co valence

Abstract

In this study, a Co3O4 catalyst is synthesised using the chitosan-assisted sol–gel method, which simultaneously regulates the grain size, Co valence and surface acidity of the catalyst through a chitosan functional group. The complexation of the free –NH2 complex inhibits particle agglomeration; thus, the average particle size of the catalyst decreases from 82 to 31 nm. Concurrently, Raman spectroscopy, hydrogen temperature-programmed reduction, electron paramagnetic resonance spectroscopy and X-ray photoelectron spectroscopy experiments demonstrate that doping with chitosan N sources effectively modulates Co2+ to promote the formation of oxygen vacancies. In addition, water washing after catalyst preparation can considerably improve the low-temperature (below 250 °C) activity of the catalyst and eliminate the side effects of alkali metal on catalyst activity. Moreover, the presence of Brønsted and Lewis acid sites promotes the adsorption of C8H8. Consequently, CS/Co3O4-W presents the highest catalytic oxidation activity for C8H8 at low temperatures (R250 °C = 8.33 μmol g−1 s−1, WHSV = 120,000 mL hr−1∙g−1). In situ DRIFTS and 18O2 isotope experiments demonstrate that the oxidation of the C8H8 reaction is primarily dominated by the Mars–van Krevelen mechanism. Furthermore, CS/Co3O4-W exhibits superior water resistance (1- and 2- vol% H2O), which has the potential to be implemented in industrial applications.