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Comprehensive Summary: The saline and buffered environment in actual wastewater imposes higher demands on Fenton and Fenton‐like catalytic systems. This study developed a MoS2 co‐catalytic Fe2O3 Fenton‐like system with controllable Lewis acid‐base sites, achieving efficient treatment of various model pollutants and actual industrial wastewater under neutral buffered environment. The acidic microenvironment structured by the edge S sites (Lewis basic sites) in the MoS2/Fe2O3 catalyst is susceptible to the influence of Lewis acidic sites constructed by Mo and Fe element, affecting catalytic performance. Optimizing the ratio of precursor amounts ensures the stable presence of the acidic microenvironment on the surface of catalyst, enabling the beneficial co‐catalytic effect of Mo sites to be realized. Furthermore, it transcends the rigid constraints imposed by the Fenton reaction on reaction environments, thereby expanding the applicability of commonplace oxides such as Fe2O3 in actual industrial water remediation. [ABSTRACT FROM AUTHOR]

Singlet oxygen (1O2) is an essential reactive species responsible for selective oxidation of organic matter, especially in Fenton‐like processes. However, due to the great limitations in synthesizing catalysts with well‐defined active sites, the controllable production and practical application of 1O2 remain challenging. Herein, guided by theoretical simulations, a series of boron nitride‐based single‐atom catalysts (BvBN/M, M=Co, Fe, Cu, Ni and Mn) were synthesized to regulate 1O2 generation by activating peroxymonosulfate (PMS). All the fabricated BvBN/M catalysts with explicit M−N3 sites promoted the self‐decomposition of the two PMS molecules to generate 1O2 with high selectivity, where BvBN/Co possessed moderate adsorption energy and d‐band center exhibited superior catalytic activity. As an outcome, the BvBN/Co‐PMS system coupled with membrane filtration technology could continuously transform aromatic alcohols to aldehydes with nearly 100 % selectivity and conversion rate under mild conditions, suggesting the potential of this novel catalytic system for green organic synthesis. [ABSTRACT FROM AUTHOR]

Copper (Cu) is evidenced to be effective for constructing advanced catalysts. In particular, Cu2O is identified to be active for general catalytic reactions. However, conflicting results regarding the true structure‐activity correlations between Cu2O‐based active sites and efficiencies are usually reported. The structure of Cu2O undergoes dynamic evolution rather than remaining stable under working conditions, in which the actual reaction cannot proceed over the prefabricated Cu2O sites. Therefore, the dynamic construction of Cu2O active sites can be developed to promote catalytic efficiency and reveal the true structure‐activity correlations. Herein, by introducing the redox pairs of Cu2+ and reducing sugar into a photocatalysis system, it is clarified that the Cu2O sub‐nanoclusters (NCs), working as novel active sites, are on‐site constructed on the substrate via a photoinduced pseudo‐Fehling's route. The realistic interfacial charge separation and transformation capacities are remarkably promoted by the dynamic Cu2O NCs under the actual catalysis condition, which achieves a milestone efficiency for nitrate‐to‐ammonia photosynthesis, including the targets of production rate (1.98±0.04 mol gCu−1 h−1), conversion ratio (94.2±0.91 %), and selectivity (98.6 %±0.55 %). The current work develops an effective strategy for integrating the active site construction into realistic reactions, providing new opportunities for Cu‐based chemistry and catalysis sciences research. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The saline and buffered environment in actual wastewater imposes higher demands on Fenton and Fenton‐like catalytic systems. This study developed a MoS2 co‐catalytic Fe2O3 Fenton‐like system with controllable Lewis acid‐base sites, achieving efficient treatment of various model pollutants and actual industrial wastewater under neutral buffered environment. The acidic microenvironment structured by the edge S sites (Lewis basic sites) in the MoS2/Fe2O3 catalyst is susceptible to the influence of Lewis acidic sites constructed by Mo and Fe element, affecting catalytic performance. Optimizing the ratio of precursor amounts ensures the stable presence of the acidic microenvironment on the surface of catalyst, enabling the beneficial co‐catalytic effect of Mo sites to be realized. Furthermore, it transcends the rigid constraints imposed by the Fenton reaction on reaction environments, thereby expanding the applicability of commonplace oxides such as Fe2O3 in actual industrial water remediation. [ABSTRACT FROM AUTHOR]

Catalytic peroxymonosulfate (PMS) activation processes don't solely rely on electron transfer from dominant metal centers due to the complicated composition and interface environment of catalysts. Herein the synthesis of a cobalt based metal-organic framework containing polyvanadate [V 4 O 12 ] 4- cluster, Co 2 (V 4 O 12 )(bpy) 2 (bpy = 4,4'-bipyridine), is presented. The catalyst demonstrates superior degradation activity toward various micropollutants, with higher highest occupied molecular orbital (HOMO), via nonradical attack. The X-ray absorption spectroscopy and density functional theory (DFT) calculations demonstrate that Co sites act as both PMS trapper and electron donor. In situ spectral characterizations and DFT calculations reveal that the terminal oxygen atoms in the [V 4 O 12 ] 4- electron sponge could interact with the terminal hydrogen atoms in PMS to form hydrogen bonds, promoting the generation of SO 5 * intermediate via both dynamic pull and direct electron transfer process. Further, Co 2 (V 4 O 12 )(bpy) 2 exhibits long-term water purification ability, up to 40 h, towards actual wastewater discharged from an ofloxacin production factory. This work not only presents an efficient catalyst with an electron sponge for water environmental remediation via nonradical pathway, but also provides fundamental insights into the Fenton-like reaction mechanism., (© 2024. The Author(s).)

It is imperative to devise effective removal strategies for high ionization potential (IP) organic pollutants in wastewater as their reduced electron-donating capacity challenges the efficiency of advanced oxidation systems in degradation. Against this backdrop, leveraging the metal-based carbon material structure meticulously, we employed metal-pyridine-N (M-N-C, M=Fe, Co, and Ni) as the electron transfer bridge. This distinctive design facilitated the ordered transfer of electrons from the adsorbent surface to the surface of high IP value pollutants, acting as a "supplement" to compensate for their deficient electron-donating capability, thereby culminating in the selective adsorption of these pollutants. Furthermore, this adsorbent also demonstrated effective removal of trace emerging contaminants (2 mg/L), displayed robust resistance to various salts, exhibited reusability, and maintained stability. These findings carry substantial implications for future carbon-based material design, offering a pathway toward exceptional adsorption performance in treating water pollution., Competing Interests: Competing interests statement:The authors declare no competing interest.

Singlet oxygen ( 1 O 2 ) is an essential reactive species responsible for selective oxidation of organic matter, especially in Fenton-like processes. However, due to the great limitations in synthesizing catalysts with well-defined active sites, the controllable production and practical application of 1 O 2 remain challenging. Herein, guided by theoretical simulations, a series of boron nitride-based single-atom catalysts (BvBN/M, M=Co, Fe, Cu, Ni and Mn) were synthesized to regulate 1 O 2 generation by activating peroxymonosulfate (PMS). All the fabricated BvBN/M catalysts with explicit M-N 3 sites promoted the self-decomposition of the two PMS molecules to generate 1 O 2 with high selectivity, where BvBN/Co possessed moderate adsorption energy and d-band center exhibited superior catalytic activity. As an outcome, the BvBN/Co-PMS system coupled with membrane filtration technology could continuously transform aromatic alcohols to aldehydes with nearly 100 % selectivity and conversion rate under mild conditions, suggesting the potential of this novel catalytic system for green organic synthesis., (© 2024 Wiley-VCH GmbH.)

Copper (Cu) is evidenced to be effective for constructing advanced catalysts. In particular, Cu 2 O is identified to be active for general catalytic reactions. However, conflicting results regarding the true structure-activity correlations between Cu 2 O-based active sites and efficiencies are usually reported. The structure of Cu 2 O undergoes dynamic evolution rather than remaining stable under working conditions, in which the actual reaction cannot proceed over the prefabricated Cu 2 O sites. Therefore, the dynamic construction of Cu 2 O active sites can be developed to promote catalytic efficiency and reveal the true structure-activity correlations. Herein, by introducing the redox pairs of Cu 2+ and reducing sugar into a photocatalysis system, it is clarified that the Cu 2 O sub-nanoclusters (NCs), working as novel active sites, are on-site constructed on the substrate via a photoinduced pseudo-Fehling's route. The realistic interfacial charge separation and transformation capacities are remarkably promoted by the dynamic Cu 2 O NCs under the actual catalysis condition, which achieves a milestone efficiency for nitrate-to-ammonia photosynthesis, including the targets of production rate (1.98±0.04 mol g Cu -1  h -1 ), conversion ratio (94.2±0.91 %), and selectivity (98.6 %±0.55 %). The current work develops an effective strategy for integrating the active site construction into realistic reactions, providing new opportunities for Cu-based chemistry and catalysis sciences research., (© 2023 Wiley-VCH GmbH.)