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• The Fenton-like Cu-PAN 3 catalysts is first synthesized by co-precipitation and carbon thermal reduction method. • Dual reaction centers are constructed around graphene-like carbon and Cu species. • The pollutants as electron donors inhibit the ineffective decomposition of H 2 O 2 at the electron-poor centers. • The pollutant removal mainly relies on the surface cleavage at the electron-poor centers. High energy consumption has seriously hindered the development of Fenton-like reactions for the removal of refractory organic pollutants in water. To solve this problem, we designed a novel Fenton-like catalyst (Cu-PAN 3) by coprecipitation and carbon thermal reduction. The catalyst exhibits excellent Fenton-like catalytic activity and stability for the degradation of various pollutants with low H 2 O 2 consumption. The experimental results indicate that the dual reaction centers (DRCs) are composed of Cu-N-C and Cu-O-C bridges between copper and graphene-like carbon, which form electron-poor/rich centers on the catalyst surface. H 2 O 2 is mainly reduced at electron-rich Cu centers to free radicals for pollutant degradation. Meanwhile, pollutants can be oxidized by donating electrons to the electron-poor C centers of the catalyst, which inhibits the ineffective decomposition of H 2 O 2 at the electron-poor centers. This therefore significantly reduces the consumption of H 2 O 2 and reduces energy consumption. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] The heterogeneous Fenton process suffers from low efficiency because of the low electron transfer cycle rate of Fe3+/Fe2+, which often consumes enormous amounts of hydrogen peroxide (H 2 O 2) or other energy. Herein, we report a novel Co-based Fenton-like catalyst (in-situ -Co-g-C 3 N 4) synthesized via the surface complexation method, in which Co species were modified in situ into the framework of the graphitic carbon nitride (g-C 3 N 4) substrate through C–O–Co chemical bonding. The catalyst exhibited higher Fenton-like catalytic activity than pure g-C 3 N 4 in the degradation of various pollutants under neutral conditions, as evidenced by the approximately 150-fold higher Fenton-like reaction rate constant of in-situ -Co-g-C 3 N 4 than that of g-C 3 N 4. Density functional theory (DFT) calculations and a series of experimental and characterization analyses revealed the interfacial reaction mechanism between H 2 O 2 , pollutants and in-situ -Co-g-C 3 N 4. During the Fenton-like reaction, the electron-poor C center on the aromatic ring of g-C 3 N 4 could capture the electrons deprived from pollutants, and subsequently deliver them to around the electron-rich Co center to efficiently reduce H 2 O 2 to hydroxyl radicals (•OH), enabling H 2 O 2 to be used efficiently for the degradation of pollutants. This study provides a strategy for improving Fenton-like degradation efficiency by effectively utilizing the energy of organic pollutants. [ABSTRACT FROM AUTHOR]

• Mesoporous reduction state cobalt species-doped silica nanospheres are first prepared. • Excellent activity is realized in mp -RSCo-SiO 2 NSs/H 2 O 2 system. • Efficient dual-pathway degradation of pollutant is achieved in Fenton-like process. • Pollutants replace H 2 O 2 as electron donors for the mp -RSCo-SiO 2 NSs system. • A new interfacial Fenton-like reaction mechanism involving pollutants is proposed. A novel heterogeneous Co-containing Fenton-like catalyst consisting of mesoporous reduction state cobalt (RSCo)-doped silica (SiO 2) nanospheres (mp -RSCo-SiO 2 NSs) was prepared by an enhanced hydrothermal process. The catalyst exhibited very high activity and stability for a series of refractory pollutant degradation in a very wide pH range of 3.1–10.9. The Fenton-like reaction rate constant of this Co-containing catalyst was approximately 290 times higher than that of Co 3 O 4 for pollutant degradation under the neutral and mild conditions. Based on the characterization, the catalyst possessed a porous nanosphere morphology, and the reduction state cobalt species, including nano-zero-valent cobalt (nZVCo) and Co2+, were found to be generated in the SiO 2 framework through forming Co O Si bonds. During the Fenton-like reaction, the electron donation effect of organic pollutants was successfully realized through the interaction of "Pollutants → Co2+/0-SiO 2 ". The obtained electrons from pollutants were transferred to the catalyst surface and captured by H 2 O 2 , resulting in the generation of hydroxyl radicals (OH). Therefore, a dual-pathway degradation of the pollutants was realized: (I) oxidation and degradation as the electron donors for the system and (II) attacking and destruction by OH radicals. This work provided a new perspective on the effective utilization of the electrons of pollutants and the improvement of Fenton reaction efficiency. [ABSTRACT FROM AUTHOR]

In common advanced oxidation processes, excess reagents and energy are often added to the reaction system to maintain the continuity of the reaction. These additions result in a large waste of resources and energy, which has become a bottleneck in the development of water treatment technology. In this study, we propose a new strategy to solve this problem based on a novel dual-reaction-center (DRC) Fe-ZnS quantum dots (Fe–ZnS QDs) catalyst that forms a non-equilibrium surface with an electron-polarized distribution. Through experimental and theoretical studies, it was verified that the activation of trace amounts of H 2 O 2 could break the energy barrier for pollutants to transfer electrons. The dissolved oxygen (DO) in the reaction system could be activated by gaining energy on the surface of the Fe–ZnS QDs catalyst, and was converted to 1O 2 to attack organic pollution. In addition, the pollutants themselves supplied electrons to H 2 O 2 through the surface of the Fe–ZnS QDs catalyst to generate more •OH radicals for pollutant degradation, thus providing two fast paths for pollutant degradation. The system could drive the reaction through a trace amount of H 2 O 2 , thereby activating DO to generate 1O 2 while effectively using the energy of pollutants. Therefore, the proposed system offers a new direction for the development of environmentally-friendly catalysts and greatly reduces the consumption of resources and energy. [Display omitted] • Fe–ZnS QDs is successfully developed as a Fenton catalyst for the first time. • The surface of ZnS QDs is regulated by trace Fe to form a non-equilibrium surface with an electron-polarized distribution. • The Fe–ZnS QDs/H 2 O 2 system exhibits excellent activity for pollutants degradation. • Inert oxygen species in reaction system are easily activated to 1O 2 to attack pollutants. [ABSTRACT FROM AUTHOR]