Ion doping to manipulate the electronic structure of the active centre has gained significant recognition as a viable approach for enhancing catalytic activity. In this study, we proposed a strategy to enhance the adsorption of oxygen-related active substances and stabilize the active site by introducing Lewis acid sites (Al3+), thereby effectively improving the adsorption of PMS and inhibiting the leaching of Co ions. Specifically, the Al-doped catalyst (Al-ZCO) prepared in this study exhibited remarkable efficiency in activating peroxymonosulfate (PMS) for levofloxacin (LEVO) degradation, with a rate constant of 0.49 min−1, which is 2.9 times higher than that of the original ZCO catalyst (0.17 min−1). Experimental and density functional theory (DFT) studies have demonstrated that Al doping effectively reduced the energy required for oxygen vacancy formation in ZCO, resulting in shorter Co-O bonds and preventing Co ion release during LEVO degradation. Additionally, DFT calculations indicated that higher density of occupied electron states in close proximity to the Fermi level enhances the ability of PMS molecules to form complexes with Al-ZCO while also influencing rehybridization between Co 3d orbital and O 2p orbital (PMS), promoting electron transfer from Co site to PMS, thus accelerating catalytic degradation reaction.

中文翻译：

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活性位点的电子结构调控以优化 Lewis 酸金属掺杂 ZnCo2O4 催化剂上的过氧一硫酸盐活化


离子掺杂以操纵活性中心的电子结构已成为增强催化活性的可行方法。在这项研究中，我们提出了一种通过引入路易斯酸位点 （Al3+） 来增强氧相关活性物质吸附并稳定活性位点的策略，从而有效改善 PMS 的吸附并抑制 Co 离子的浸出。具体来说，本研究制备的 Al-Doped 催化剂 （Al-ZCO） 在激活过氧一硫酸盐 （PMS） 以降解左氧氟沙星 （LEVO） 方面表现出显着的效率，速率常数为 0.49 min-1，比原始 ZCO 催化剂 （0.17 min-1） 高 2.9 倍。实验和密度泛函理论 （DFT） 研究表明，Al 掺杂有效地降低了 ZCO 中氧空位形成所需的能量，导致更短的 Co-O 键并防止 LEVO 降解过程中的 Co 离子释放。此外，DFT 计算表明，靠近费米能级的更高密度的占据电子态增强了 PMS 分子与 Al-ZCO 形成复合物的能力，同时也影响了 Co 3d 轨道和 O 2p 轨道 （PMS） 之间的再杂化，促进电子从 Co 位点转移到 PMS，从而加速催化降解反应。