The heterogeneous Fenton-like reaction has been widely used in water purification and environmental remediation due to the highly reactive nature of hydroxyl radicals. Nevertheless, the intrinsic structure–activity relationship for heterogeneous Fenton-like reaction catalysts remains to be clarified. Metal/nitrogen/carbon (M/N/C) single-atom catalysts (SACs) provide an ideal opportunity to reveal the relationship between the structure and activity. In this work, the detailed catalytic mechanism and activity of H₂O₂ decomposition on p-block main-group metal/nitrogen/carbon (PM/N/C) catalysts were investigated systematically. A volcano relationship between the catalytic activity and the adsorption energies of reaction intermediates was found for H₂O₂ decomposition on PM/N/C SACs. PM-N₂C₂ and PM-C₄ exhibit higher H₂O₂ decomposition activity than PM-N₄, indicating that reducing the N/C ratio in the coordination environment can effectively adjust the catalytic activity. By altering the N/C coordination environment, it is possible to modify the p-band position of p-block main-group metal atoms in PM/N/C SACs, thereby enhancing the catalytic activity of H₂O₂ decomposition.

中文翻译：

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p-嵌段金属-氮-碳单原子催化剂在非均相Fenton-like反应中的理论研究


由于羟基自由基的高反应性，非均相 Fenton 样反应已广泛用于水净化和环境修复。然而，非均相 Fenton 类反应催化剂的内禀构效关系仍有待阐明。金属/氮/碳 （M/N/C） 单原子催化剂 （SAC） 为揭示结构和活性之间的关系提供了理想的机会。本工作系统研究了 H₂O₂ 在 p 嵌段主族金属/氮/碳 （PM/N/C） 催化剂上分解的详细催化机理和活性。发现 PM/N/C SAC 上 H₂O₂ 分解反应中间体的催化活性与吸附能之间存在火山岩关系。PM-N₂C₂ 和 PM-C₄ 表现出比 PM-N₄ 更高的 H₂O₂ 分解活性，表明在配位环境中降低 N/C 比可以有效调节催化活性。通过改变 N/C 配位环境，可以改变 PM/N/C SAC 中 p 区主族金属原子的 p 波段位置，从而增强 H₂O₂ 分解的催化活性。