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Water molecules are actively involved in many catalytic oxidation processes, which require the construction of highly active sites for their activation to accelerate the reaction rate, especially over non‐noble metal catalysts. Herein, K species is embeded into the natural 2*2 channel of α‐MnO2 by a hydrothermal coupled molten salt method, which would make these K species behave in an electron‐rich state and provide more electrons for the activation of water molecules. Compared with surface K modification (namely, the electron‐deficient K species), channel K confinement can lower the activation energy barrier of H2O dissociation on α‐MnO2 to generate hydroxyl species with more nucleophilic oxygen atoms, contributing to the superior HCHO catalytic oxidation activity with a fourfold enhancement. The internal relationship among the confined channel, K species, and catalytic performance is systematically elucidated at the molecular level. This work offers a new ion confinement method and opens up new avenues to construct electron‐rich metal sites with channel structures for the activation of water molecules. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Efficient molecular oxygen activation is crucial for catalytic oxidation reaction, but highly depends on the construction of active sites. In this study, we demonstrate that dual adjacent Fe atoms anchored on MnO2 can assemble into a diatomic site, also called as MnO2-hosted Fe dimer, which activates molecular oxygen to form an active intermediate species Fe(O = O)Fe for highly efficient CO oxidation. These adjacent single-atom Fe sites exhibit a stronger O2 activation performance than the conventional surface oxygen vacancy activation sites. This work sheds light on molecular oxygen activation mechanisms of transition metal oxides and provides an efficient pathway to activate molecular oxygen by constructing new active sites through single atom technology. Efficient oxygen activation is crucial for catalytic oxidation reaction, but highly depends on the construction of active sites. Here, dual adjacent Fe atoms anchored on MnO2 can assemble into a diatomic site, which activates molecular oxygen to form an active intermediate species Fe(O = O)Fe for CO oxidation. [ABSTRACT FROM AUTHOR]

A series of Ag3PO4/Bi2MoO6 p-n heterojunctions were assembled via the thin Bi2MoO6 nanosheets attached to the surface of rhombic dodecahedral Ag3PO4. The self-optimized Ag+/Ag0 pairs existed in the as-prepared heterojunction which are regarded as charge transmission bridge to accelerate the reaction. The samples presented much higher photocatalytic activity for the degradation of the target pollutions (completely degradation under solar light illuminating of 70 min for rhodamine B, 80 min for aureomycin and 70 min for tetracycline). It was found during the recycle test, photocatalytic performance of Ag3PO4/Bi2MoO6 underwent a successive increase since the second cycle in which the completely degradation of RhB was achieved after only 60 min visible light irradiation, confirming the composite is reusable with well stability. The oxidative mechanism was carefully investigation based on the scavengers trapping test, ESR spectra, XPS spectrum, photocurrent responses, and electrochemical impedance spectroscopy analysis. It proved Ag0 gradually generated from the as-prepared composite under solar light illuminating is fixed at an optimized content. The charge transfer was consequentially enhanced during the suitable level turning of Ag+/Ag0 pairs. Mediated by Ag0 sandwiched in p-n junction, the active species of the present photooxidative reaction experienced various period from ·OH and h+ in the initial reaction to the additional ·O2− in the successive recycle experiment owing to generation of the rectifying contact and Schottky junction. This study provides a new cognition for the improved reusability of the photocorrosion materials via the mutual transformation of metal monomers and ions. [ABSTRACT FROM AUTHOR]

In this investigation, phosphotungstic acid (H3PW12O40) was successfully self-assembly implanted into the interspace of K4Nb6O17 nanosheet via an impregnation method to form an adsorption-photocatalytic composite, in which n-type semiconductor K4Nb6O17 was selected as photo-electron emitter and H3PW12O40 was particularly used as an electronic transmitter. By characterizing with X-ray diffraction (XRD), transmission (TEM), scan electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and FT-IR spectrum (FT-IR), it confirmed that H3PW12O40 (HPW) was converted to the insoluble tiny particles of K3PW12O40 (KPW) with the remained primary Keggin group via an ion-exchanged H+ of HPW with K+ in K4Nb6O17 in the implanted process and was firmly bound to the surface of K4Nb6O17 to form well sandwich structure. UV-vis diffuse reflectance spectroscopy revealed that the band gap of K4Nb6O17-K3PW12O40 have a slight red shift compared with the single K4Nb6O17. Its adsorption-photocatalytic properties were evaluated with the removal of tetracycline as model reaction. Compared with pure K4Nb6O17, tetracycline removal rate can be significantly improved for the as-prepared sandwich. Importantly, the removal could still maintain 70% after five reuses in recycle tests at an acidic solution, inferring a good stability which was mainly ascribed to the formation of water-insoluble K3PW12O40. The separation and transfer process of photogenerated electrons were investigated by surface photovoltage spectroscopy (SPV). It proposed that the KPW anchored firmly on the interlayers of K4Nb6O17 through a O-K-O bridge plays a significantly role in promoting the separation of the photogenerated carriers and preventing the leakage and agglomeration of HPW. The present results showed that the strategy of the phosphotungstic acid binding in situ to K4Nb6O17 was favorable to promote the hetero-photocatalytic efficiency as well as reusability.Mechanism for tetracycline photodegradation over the K4Nb6O17-KPW photocatalytic system [ABSTRACT FROM AUTHOR]