A sequence of alkali metal cation-exchanged Co metal-organic frameworks(Co-MOFs),therein after denoted as M@Co-MOF,M=Na+,K+,Rb+,and Cs+,was prepared and used as the precursors to obtain the corresponding alkali doped cobalt oxide(defined as M/Co3O4,M=Na+,K+,Rb+,and Cs+) through calcination under air atmosphere.The cobalt oxide modified by uniform alkali metals exhibited a significant promotion of catalytic activity for CO oxidation.The activity of M/Co3O4 decreased in the order of Cs+＞Na+＞K+＞Rb+.Experimental and theoretical results revealed that the anionic skeleton of Co-MOF could facilely adsorb alkali metal cations and play a crucial role in the formation of highly uniform alkali doped cobalt oxide.The further characterizations,such as temperature-programmed reduction of H2(H2-TPR),oxygen temperature-programmed desorption(O2-TPD),X-ray photoelectron spectroscopy(XPS),and in situ diffuse reflectance infrared Fourier transform(DRIFT) spectra demonstrated that the enhanced catalytic activity is originated from the interfacial electron transfer as well as weakened the Co-O bond strength,which promoted oxygen desorption from Co3O4 and formation of cobalt species with the lower valence state.The Cs/Co3O4 catalyst was maintained for 60 h without deactivation and still showed a high activity in the presence of water.