Low Concentration of Peroxymonosulfate Triggers Dissolved Oxygen Conversion over Single Atomic Fe-N3 O1 Sites for Water Decontamination.

Achieving satisfactory organic pollutant oxidation with a low concentration of peroxymonosulfate (PMS) is vital for persulfate-involved advanced oxidation processes to reduce resource consumption and avoid excessive sulfate anion (SO4 2- ) production. Herein, efficient conversion of dissolved oxygen (DO) over single-atomic Fe-N3 O1 sites anchored on carbon nitride for efficient contaminant degradation is fulfilled, triggered by a low concentration of PMS (0.2 mm). Experimental and theoretical results reveal that the preferentially adsorbed PMS onto atomic Fe-N3 O1 center can deliver electrons toward the single Fe atom to increase its electron density to trigger DO reduction into superoxide radical (O2 • - ) and successive transformation into singlet oxygen (1 O2 ), which is quite different from the conventional PMS activation process mostly depending on PMS itself function for reactive oxygen species generation. On the other hand, PMS with high concentration could occupy active Fe-N3 O1 sites to hamper DO conversion and further produce massive SO4 2- . A couple of -Fe-CN0.05 -and slight PMS is effective for actual kitchen wastewater remediation and long-term bisphenol A degradation. This work elucidates the triggering role of low-concentration PMS in DO conversion over a single-atom Fe catalyst, which can inspire the development of resource-saving, cost-effective, and environmentally-friendly catalytic oxidation systems for environmental restoration.

Turning the Inert Element Zinc into an Active Single-Atom Catalyst for Efficient Fenton-Like Chemistry.

Amongst various Fenton-like single-atom catalysts (SACs), the zinc (Zn)-related SACs have been barely reported due to the fully occupied 3d10 configuration of Zn2+ being inactive for the Fenton-like reaction. Herein, the inert element Zn is turned into an active single-atom catalyst (SA-Zn-NC) for Fenton-like chemistry by forming an atomic Zn-N4 coordination structure. The SA-Zn-NC shows admirable Fenton-like activity in organic pollutant remediation, including self-oxidation and catalytic degradation by superoxide radical (O2 ⋅- ) and singlet oxygen (1 O2 ). Experimental and theoretical results unveiled that the single-atomic Zn-N4 site with electron acquisition can transfer electrons donated by electron-rich pollutants and low-concentration PMS toward dissolved oxygen (DO) to actuate DO reduction into O2 ⋅- and successive conversion into 1 O2 . This work inspires an exploration of efficient and stable Fenton-like SACs for sustainable and resource-saving environmental applications.

Electron Delocalization Realizes Speedy Fenton-Like Catalysis over a High-Loading and Low-Valence Zinc Single-Atom Catalyst.

A zinc (Zn)-based single-atom catalyst (SAC) is recently reported as an active Fenton-like catalyst; however, the low Zn loading greatly restricts its catalytic activity. Herein, a molecule-confined pyrolysis method is demonstrated to evidently increase the Zn loading to 11.54 wt.% for a Zn SAC (ZnSA -N-C) containing a mixture of Zn-N4 and Zn-N3 coordination structures. The latter unsaturated Zn-N3 sites promote electron delocalization to lower the average valence state of Zn in the mix-coordinated Zn-Nx moiety conducive to interaction of ZnSA -N-C with peroxydisulfate (PDS). A speedy Fenton-like catalysis is thus realized by the high-loading and low-valence ZnSA -N-C for PDS activation with a specific activity up to 0.11 min L-1 m-2 , outstripping most Fenton-like SACs. Experimental results reveal that the formation of ZnSA -N-C-PDS* complex owing to the strong affinity of ZnSA -N-C to PDS empowers intense direct electron transfer from the electron-rich pollutant toward this complex, dominating the rapid bisphenol A (BPA) elimination. The electron transfer pathway benefits the desirable environmental robustness of the ZnSA -N-C/PDS system for actual water decontamination. This work represents a new class of efficient and durable Fenton-like SACs for potential practical environmental applications.