The efficient and selective generation of highly active ˙OH in a heterogeneous Fenton-like process is closely related to the spatial arrangement of active sites, local electron density of reactive atoms, and configuration of H₂O₂ adsorption to the active centers. Herein, a facile interlayer-release approach for the synthesis of a Cu single atom coordinated defect-rich Fe₂O₃/CuFeO₂ heterogeneous photo-Fenton-like catalyst (Cu–O_v–Fe₂O₃/CuFeO₂) with abundant atomically exposed Cu–O_v–Fe sites is developed. The asymmetric Cu–O_v–Fe sites, coupled with their acidic microenvironment, significantly enhance the adsorption of the Lewis-base H₂O₂ in a side-on configuration. This, in turn, promotes the homolytic cleavage of O–O bonds and selectively generates ˙OH. Fe₂O₃/CuFeO₂ and agglomerated Cu clusters serve as the photosensitizers for efficient generation of photoexcited electrons, which are driven by a built-in electric field to the defect-rich Fe₂O₃ shell. Upon being trapped by the oxygen vacancies of Fe₂O₃, the electrons then flow directionally and get concentrated at the bimetallic Cu–O_v–Fe active sites, enhancing their electron density. The formation of the highly condensed localized electron density greatly improves the H₂O₂ activation kinetics. Benefitting from the excellent synergic effects of photocatalysis, single-atom catalysis, and asymmetric bimetallic activation effects, the well-designed Cu–O_v–Fe₂O₃/CuFeO₂ exhibits record-breaking outstanding activity with TOF as high as 1.168 h⁻¹ (99% degradation of phenol in 15 min), a remarkable selectivity of 78% for ˙OH, excellent durability with only 8% loss of activity after four runs and 23% loss after eight runs, and wide pH adaptability ranging from pH 4.5 to 9.

中文翻译：

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锚定在异质光催化剂上的铜单原子的层间释放合成，用于构建具有超快 H2O2 活化动力学的 Cu-Ov-Fe 双金属活性位点


非均相类芬顿过程中高活性˙OH的高效选择性生成与活性位点的空间排列、反应原子的局部电子密度以及H ₂ O ₂吸附到活性中心的构型密切相关。在此，一种简便的层间释放方法用于合成Cu单原子配位的富含缺陷的Fe ₂ O ₃ /CuFeO ₂非均相类光芬顿催化剂（Cu–O _v –Fe ₂ O ₃ /CuFeO ₂ ），该催化剂具有丰富的开发了原子暴露的 Cu-O _v -Fe 位点。不对称的 Cu-O _v- Fe 位点与其酸性微环境相结合，显着增强了侧向配置中路易斯碱 H ₂ O ₂的吸附。这反过来又促进 O-O 键的均裂并选择性地生成 ˙OH。 Fe ₂ O ₃ /CuFeO ₂和团聚的Cu簇作为光敏剂，有效产生光生电子，这些电子由内置电场驱动到富含缺陷的Fe ₂ O ₃壳层。 一旦被Fe ₂ O ₃的氧空位捕获，电子就会定向流动并集中在双金属Cu-O _v -Fe活性位点，从而增强其电子密度。高度凝聚的局域电子密度的形成极大地改善了H ₂ O ₂的活化动力学。受益于光催化、单原子催化和不对称双金属活化效应的优异协同效应，精心设计的Cu-O _v -Fe ₂ O ₃ /CuFeO ₂表现出破纪录的优异活性，TOF高达1.168 h ^{- 1} （15 分钟内苯酚降解 99%），对 ˙OH 的选择性高达 78%，出色的耐久性，四次运行后活性仅损失 8%，八次运行后活性损失仅 23%，pH 值适应性广，范围为 pH 4.5到 9。