Highly Uniform Alkali Doped Cobalt Oxide Derived from Anionic Metal-Organic Framework: Improving Activity and Water Tolerance for CO Oxidation

doi:10.1007/s40242-020-0024-3

Abstract

Abstract: 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.

Key words: Anionic framework, Alkali metal, CO oxidation, M/Co₃O₄, Metal-organic framework precursor

LEI Huijin, ZHANG Xinlu, JIN Jiongke, WANG Shuhua, DING Shunmin, ZHANG Ning, CHEN Chao. Highly Uniform Alkali Doped Cobalt Oxide Derived from Anionic Metal-Organic Framework: Improving Activity and Water Tolerance for CO Oxidation[J]. Chemical Research in Chinese Universities, 2020, 36(5): 946-954.

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