关键词: 水煤气变换, 四氧化三铁, 密度泛函理论, 机理

Water gas shift (WGS) reaction is of great importance for industrial hydrogen production. Using density functional theory calculation, we systematically investigated the catalytic processes of WGS on Fe₃O₄ (111) surface. Our calculations indicate that the activation barrier of the redox mechanism is much larger than that of the associative mechanism, suggesting the intermediates of WGS prefer to undergo the associative pathway. H atoms recombination towards H₂ is the rate determining step with an activation barrier of 1.29 eV, in good agreement with reported experimental values. The results provide rational explanations to the experimental phenomena of WGS reaction, and the improvement of Fe₃O₄(111) catalyst was also discussed.

Key words: water gas shift reaction, Fe₃O₄, density functional theory, mechanism