Atomic-Scale Insights into the Low-Temperature Oxidation of Methanol Over a Single-Atom Pt1-Co3o4 Catalyst

Abstract

Heterogeneous catalysts with single-atom active sites offer a means of expanding the industrial application of noble metal catalysts. Herein, we present an atomically dispersed Pt1-Co3O4 catalyst, which exhibits an exceptionally high catalytic activity for the total oxidation of various representative volatile organic compounds. Experimental and theoretical investigations indicated that this catalyst consisted of Pt sites with a large proportion of occupied high electronic states. These sites exhibited a strong affinity for the 3d orbital of Co, which increased electron transfer from Pt to Co3O4 and ultimately, accelerated the rate of oxygen vacancy regeneration. In turn, this was determined to promote the co-adsorption of probe VOC and O2. With methanol, DFT calculations confirmed that the electron transfer over the oxygen vacancy reduces both the methanol adsorption energy and activation barriers for methanol oxidation, which was proposed to significantly enhance the dissociation of the C-H bond in the methanol decomposition reaction. This investigation serves as a solid foundation for characterizing and understanding single-atom catalysts for heterogeneous oxidation reactions.