Hydrogen, the fuel of PEMFC, is produced via the reforming of hydrocarbons and water-gas shift reaction were contains 0.5vol %-2.0 vol % CO, which can poison Pt anode.Therefore, the concentration of CO must be reduced to below 100ppm [1].It is known that the preferential oxidation (PROX) of CO in H2-rich is the simplest and cost-effective routes for the removal of CO in H2 [2].For the catalysts, the Co3O4 was known to exhibit good catalytic performance for the oxidation of CO by O2 at lower temperatures.And the manganese catalysts recognize as a promoter cobalt oxide and copper oxide catalysts.