Highly enhanced room-temperature single-atom catalysis of two-dimensional organic-inorganic multiferroics Cr(half-fluoropyrazine)(2) for CO oxidation

二维有机-无机多铁性材料Cr(半氟吡嗪)₂在室温下对CO氧化具有显著增强的单原子催化活性

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Abstract

In modern chemistry, the development of highly efficient room-temperature catalysts is of great significance and remains a long-standing challenge in various typical reactions. Here, we theoretically demonstrate that the two-dimensional (2D) multiferroic, Cr(half-fluoropyrazine)(2) [Cr(h-fpyz)(2)], is a promising single-atom catalyst (SAC) operating at room temperature for CO oxidation. The rate-limiting barrier is merely 0.325 eV, leading to a reaction rate (i.e., 3.47 × 10(6) s(-1)) of six orders of magnitude higher than its monoferroic derivative [Cr(pyz)(2)], due to the synergetic effects of two aspects. First, the more flexible ligand rotations in Cr(h-fpyz)(2) facilitate the activation of O(2) molecule, simultaneously enhancing the charge transfer and spin-accommodation process. Second, on Cr(h-fpyz)(2), O(2) adsorption induces a distinctly lower local positive electric field, reducing the electrostatic repulsion of the polar CO molecule. These findings may also pave the way for establishing highly efficient SAC platforms based on 2D multiferroics where multidegree of freedom (e.g., spin, polarity) synergistically matter.

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