Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072, P. R. China.
Yangtze Delta Region Institute (Huzhou), School of Physics, University of Electronic Science and Technology of China, Huzhou, 313001, P. R. China.
Small. 2022 Aug;18(33):e2203269. doi: 10.1002/smll.202203269. Epub 2022 Jul 24.
Persistent organic pollutants (POPs) have a huge impact on human health due to their high toxicity and non-degradability. It is still of great difficulty to develop highly efficient catalysts toward the degradation of POPs. Herein, it is reported that regulating electronic structure of quasi-single atomic ferric iron (Fe(III)) in the VO support through the electronic metal-support interaction (EMSI) is a versatile strategy to enhance the catalytic activity. Activated Fe(III) can react with peroxydisulfate (PDS) to produce both radicals and high-valent iron (HVFe) simultaneously for the efficient and fast degradation of POPs. Density functional theory (DFT) calculations prove that the influence of EMSI promotes the electrons on Fe(III) 3d-bond center moving close to the Fermi level, facilitating the charge transfer from Fe(III) to the adsorbate. Through the control experiments, both the radical path by PDS and the HVFe path aroused by the EMSI are confirmed in the POP degradation process. Consequently, the Fe/VO catalyst exhibits record-breaking catalytic activity with the k-value as high as 56.7, 43.3 µmol s g for p-chlorophenol and 2,4-dichlorophenol degradation, respectively.
持久性有机污染物（POPs）由于其高毒性和不可降解性，对人类健康有巨大影响。开发高效催化剂来降解 POPs 仍然具有很大的难度。本文报道了通过电子金属-载体相互作用（EMSI）调节 VO 载体中类单原子铁（Fe(III)）的电子结构，是增强催化活性的一种通用策略。活化的 Fe(III) 可以与过二硫酸盐（PDS）反应，同时产生自由基和高价铁（HVFe），从而高效快速地降解 POPs。密度泛函理论（DFT）计算证明，EMSI 的影响促进了 Fe(III) 3d 键中心上的电子向费米能级移动，促进了 Fe(III) 向吸附物的电荷转移。通过控制实验，在 POP 降解过程中证实了由 PDS 引起的自由基途径和由 EMSI 引起的 HVFe 途径。因此，Fe/VO 催化剂表现出创纪录的催化活性，其 k 值分别高达 56.7、43.3 µmol s g 用于降解对氯苯酚和 2,4-二氯苯酚。
