Atomic‐Layered Cu₅ Nanoclusters on FeS₂ with Dual Catalytic Sites for Efficient and Selective H₂O₂ Activation

Abstract

Regulating the distribution of reactive oxygen species generated from H2O2 activation is the prerequisite to ensuring the efficient and safe use of H2O2 in the chemistry and life science fields. Herein, we demonstrate that constructing a dual Cu−Fe site through the self‐assembly of single‐atomic‐layered Cu5 nanoclusters onto a FeS2 surface achieves selective H2O2 activation with high efficiency. Unlike its unitary Cu or Fe counterpart, the dual Cu−Fe sites residing at the perimeter zone of the Cu5/FeS2 interface facilitate H2O2 adsorption and barrierless decomposition into ⋅OH via forming a bridging Cu‐O‐O‐Fe complex. The robust in situ formation of ⋅OH governed by this atomic‐layered catalyst enables the effective oxidation of several refractory toxic pollutants across a broad pH range, including alachlor, sulfadimidine, p‐nitrobenzoic acid, p‐chlorophenol, p‐chloronitrobenzene. This work highlights the concept of building a dual catalytic site in manipulating selective H2O2 activation on the surface molecular level towards efficient environmental control and beyond.

Diatomic Pd−Cu Metal‐Phosphorus Sites for Complete N≡N Bond Formation in Photoelectrochemical Nitrate Reduction

“…Meanwhile, referring to the WT plots of Cu foil, Cu 2 O, and CuO (Figures 2d-f), there is no WT maximum at 7.0 Å À 1 and 8.1 Å À 1 , indicating the negligible amount of CuÀ O bonds and CuÀ Cu bonds. [19] Similarly, the WT maximum at 5.6 Å À 1 and 10.3 Å À 1 in PdCuÀ P 4 are attributed to the PdÀ P bonds and PdÀ Cu bonds, respectively (Figure 2m). There is no WT maximum at 7.2 Å À 1 and 9.7 Å À 1 , indicating that the amount of PdÀ O bonds and PdÀ Pd bonds is very low.…”

“…The WT maximum at 5.5 Å −1 and 6.7 Å −1 in PdCu−P 4 are attributed to the Cu−P bonds and Cu−Pd bonds, respectively, which are very consistent with the EXAFS results (Figure 2g). Meanwhile, referring to the WT plots of Cu foil, Cu 2 O, and CuO (Figures 2d–f), there is no WT maximum at 7.0 Å −1 and 8.1 Å −1 , indicating the negligible amount of Cu−O bonds and Cu−Cu bonds [19] . Similarly, the WT maximum at 5.6 Å −1 and 10.3 Å −1 in PdCu−P 4 are attributed to the Pd−P bonds and Pd−Cu bonds, respectively (Figure 2m).…”

Boosting Benzene Oxidation with a Spin‐State‐Controlled Nuclearity Effect on Iron Sub‐Nanocatalysts

“…For the BOR with H 2 O 2 , the efficient activation of H 2 O 2 to generate activated oxygen species (AOSs) adsorbed on the metal sites, such as hydroxyl radicals (⋅OH*, * refers to the metal active site), hydroperoxyl radicals (⋅OOH*), superoxide radicals (⋅O 2 − *), and singlet oxygen ( 1 O 2 *), is a prerequisite and crucial for subsequent selective C−H activation of benzene. Previous reports demonstrate that the types of AOSs generated from H 2 O 2 are predominantly mediated by the atomic and electronic configuration of metal active sites [17] . The effects of various radical scavengers on BOR were determined to study the H 2 O 2 activation manner on Fe x ‐NOC.…”

“…Previous reports demonstrate that the types of AOSs generated from H 2 O 2 are predominantly mediated by the atomic and electronic configuration of metal active sites. [17] The effects of various radical scavengers on BOR were determined to study the H 2 O 2 activation manner on Fe x -NOC. As shown in Figure 3b, benzene conversions over Fe x -NOC (x = 1, 2, and 4) all nearly remain unchanged after the addition of BQ, TEMP, K 2 S 2 O 8 , and BHT, thus revealing that * O 2 À , 1 O 2 , electronic and alkyl radicals were not the main reactive intermediates or species.…”

Boosting Benzene Oxidation with a Spin‐State‐Controlled Nuclearity Effect on Iron Sub‐Nanocatalysts

“…Previous reports demonstrate that types of AOSs generated from H 2 O 2 are predominantly mediated by the atomic and electronic configuration of metal active sites. [17] The effects of various radical scavengers on BOR were determined to study the H 2 O 2 activation manner on Fe x -NOC. As shown in Figure 3b, benzene conversions over Fe x -NOC (x = 1, 2, and 4) all nearly remain unchanged after the addition of BQ, TEMP, K 2 S 2 O 8 , and BHT, thus revealing that * O 2 À , 1 O 2 , electronic and alkyl radicals were not the main reactive intermediates or species.…”