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For the sustainable reutilization of poultry feces (PF) to reduce environmental pollution, we present a novel approach for converting PF into a highly effective catalyst, consisting of trace copper (Cu) and sulfur (S) linked with ordered graphitized carbon (CS/CPF) for wastewater purification. Raman and EPR results verified that the disorderly organic matters in PF are transformed into orderly graphene structures that complexed with Cu to form large numbers of electron-poor/rich microregions on CS/CPF surface. The electrons from electron-rich organic pollutants can be directly captured by dissolved oxygen (DO) to produce abundant reactive oxygen species due to the enhanced electron polarization via the construction of Cu-S-C bond bridge on CS/CPF surface, which greatly enhance the removal efficiency of pollutants. CS/CPF achieves 100% removal for 2,4-dichlorophenoxyacetic acid (2,4-D) in just 10 min after adding trace peroxymonosulfate (PMS), keeping efficient catalytic activity after continuous reactions for 240 h. This strategy offers a practical and sustainable solution for the efficient resource recovery of poultry feces., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Excessive consumption of energy and resources is a major challenge in wastewater treatment. Here, a novel heterogeneous Fenton-like catalyst consisting of Cu-doped graphene-like catalysts (Cu-GCD NSs) was first synthesized by an enhanced carbothermal reduction of β-cyclodextrin (β-CD). The catalyst exhibits excellent Fenton-like catalytic activity for the degradation of various pollutants under neutral conditions, accompanied by low H 2 O 2 consumption. The results of structural characterization and theoretical calculations confirmed that the dual reaction centers (DRCs) were constructed on Cu-GCD NSs surface through C-O-Cu bonds supported on zero-valent copper species, which play a significant role in the high-performance Fenton-like reaction. The pollutants that served as electron donors were decomposed in the electron-poor carbon centers, whereas H 2 O 2 and dissolved oxygen obtained these electrons in the electron-rich Cu centers through C-O-Cu bonds, thereby producing more active species. This study demonstrates that the electrons of pollutants can be efficiently utilized in Fenton-like reactions by DRCs on the catalyst surface, which provides an effective strategy to improve Fenton-like reactivity and reduce H 2 O 2 consumption., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationship that could have appeared to influence the work reported in this article., (Copyright © 2022. Published by Elsevier B.V.)

The stable structure and toxic effect of refractory organic pollutants in wastewater lead to the problem of high energy consumption in water treatment technology. Herein, we propose a synergistic purification of refractory wastewater driven by microorganisms and surface microelectric fields (SMEF) over a dual-reaction-center (DRC) catalyst HCLL-S8-M prepared by an in situ growth method of carbon nitride on the Cu-Al 2 O 3 surface. Characterization techniques demonstrate the successful construction of SMEF with strong electrostatic force over HCLL-S8-M based on cation-π interactions between metal copper ions and carbon nitride rings. With the catalyst as the core filler, an innovative fixed bed bioreactor is constructed to purify the actual kitchen-oil wastewater. The removal efficiency of the wastewater even with a very low biodegradability (BOD 5 /COD = 0.33) can reach 60% after passing through this bioreactor. An innovative reaction mechanism is revealed for the first time that under the condition of a small amount of biodegradable organic matter, the SMEF induces the enrichment of electric active microorganisms (Desulfobulbus and Geobacter) in the wastewater, accelerates the interspecies electron transfer of intertrophic metabolism with the biodegradable bacteria through the extracellular electron transfer mechanism such as cytochrome C and self-secreted electron shuttle. The electrons of the refractory organic pollutants adsorbed on the surface of the catalyst are delocalized by the SMEF, which can be directly utilized by microorganisms through EPS conduction. The SMEF generated by electron polarization can maximize the utilization of pollutants and microorganisms in wastewater and further enhance degradation without adding any external energy, which is of great significance to the development of water self-purification technology., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Improper disposal of waste biomass and an increasing number of emerging contaminants (ECs) in water environment are universal threats to the global environment. Here, we creatively propose a sustainable strategy for the direct resource transformation of livestock manure (LM) into an innovative catalyst (Fe-CCM) for water self-purification with zero external consumption. ECs can be rapidly degraded in this self-purification system at ambient temperature and atmospheric pressure, without any external oxidants or energy input, accompanied by H 2 O and dissolved oxygen (DO) activation. The performance of the self-purification system is not affected by various types of salinity in the wastewater, and the corresponding second-order kinetic constant is improved 7 times. The enhanced water self-purification mechanism reveales that intermolecular forces between anions and pollutants reinforce electron exchange between pollutants and metal sites on the catalyst, further inducing the utilization of the intrinsic energy of contaminants, H 2 O, and DO through the interfacial reaction. This work provides new insights into the rapid removal of ECs in complicated water systems with zero external consumption and is expected to advance the resource utilization of livestock waste.

Herein, a novel metal-free catalyst consisting of multiporous oxygen-rich carbon-nitrogen graphene-like nanosheets (O LAA -CN NSs) is first developed through a staged temperature-programmed calcination of l-ascorbic acid (LAA)-modified dicyandiamide precursor. It is found that the oxygen species from l-ascorbic acid (O LAA ) are introduced into the graphene-like basic matrix and replace partial N atoms to form the COC-R structure, leading to the non-uniform distribution of electrons on the catalyst surface, and the formation of electron-rich centers around the COC microareas according to a series of characterization techniques. As a result, O LAA -CN NSs exhibits excellent performance for refractory pollutant removal in the presence of peroxymonosulfate (PMS) and dissolved oxygen. Some pollutants with complex structures are even completely degraded within only 1 min. The interface reaction mechanism is further revealed that PMS mainly acts as an active inducer to drive the electron donation of pollutants over O LAA -CN NSs. These electrons are finally utilized by dissolved oxygen to generate reactive oxygen species (ROS) through the interface process. This reaction system results in pollutants that can either be cleaved directly by surface oxidation process or degraded by the attack of the generated ROS, such as singlet oxygen ( 1 O 2 ) and superoxide radicals (O 2 •- ), through oxygen activation, which significantly reduces the resource and energy consumption in advanced wastewater treatment by harnessing the energy of pollutants and dissolved oxygen in the water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

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 1 O 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 1 O 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., (Copyright © 2021 Elsevier B.V. All rights reserved.)

To achieve high efficiency and low consumption for water treatment in the Fenton reaction, we use the surface oxygen vacancies (OVs) as the electron temporary residences to construct a dual-reaction-center (RDC) Fenton-like catalyst with abundant surface electron-rich/poor areas consisting of OV-rich Co-ZnO microparticles (OV-CoZnO MPs). The lattice-doping of Co into ZnO wurtzite results in the formation of OVs with unpaired electrons (electron-rich OVs) and electron-deficient Co 3+ sites according to the structural and electronic characterizations. Both experimental and theoretical calculations prove that the electron-rich OVs are responsible for the capture and reduction of H 2 O 2 to generate hydroxyl radicals, which quickly degrades pollutants, while a large amount of pollutants are adsorbed at the electron-deficient Co 3+ sites and act as electron donors for the system, accompanied by their own oxidative degradation. The electrons obtained from the pollutants in the electron-deficient sites are transferred to the OVs through the internal bond bridge to achieve the balance of electron gain/loss. Through this process, pollutants are efficiently converted and degraded by multiple pathways in a wide range of pH (4.5-9.5). The reaction rate of the OV-CoZnO MPs/H 2 O 2 system is increased by ∼17 times compared with the non-DRC system. This discovery provides a sustainable strategy for pollutant utilization, which shows new implications for solving the troublesome issues of the Fenton reaction and for developing novel environmental remediation technologies.

Oxygen-doped graphitic carbon nitride (O-CN) was fabricated via a facile thermal polymerization method using urea and oxalic acid dihydrate as the graphitic carbon nitride precursor and oxygen source, respectively. Experimental and theoretical results revealed that oxygen doping preferentially occurred on the two-coordinated nitrogen positions, which create the formation of low and high electron density areas resulting in the electronic structure modulation of O-CN. As a result, the resultant O-CN exhibits enhanced catalytic activity and excellent long-term stability for peroxymonosulfate (PMS) activation toward the degradation of organic pollutants. The O-CN with modulated electronic structure enables PMS oxidation over the electron-deficient C atoms for the generation of singlet oxygen ( 1 O 2 ) and PMS reduction around the electron-rich O dopants for the formation of hydroxyl radical ( • OH) and sulfate radical (SO 4 •- ), in which 1 O 2 is the major reactive oxygen species, contributing to the selective reactivity of the O-CN/PMS system. Our findings not only propose a novel PMS activation mechanism in terms of simultaneous PMS oxidation and reduction for the production of nonradical and radical species but also provide a valuable insight for the development of efficient metal-free catalysts through nonmetal doping toward the persulfate-based environmental cleanup.

Carbon nitride compounds (CN) complexed with the in-situ-produced Cu(II) on the surface of CuAlO 2 substrate (CN-Cu(II)-CuAlO 2 ) is prepared via a surface growth process for the first time and exhibits exceptionally high activity and efficiency for the degradation of the refractory pollutants in water through a Fenton-like process in a wide pH range. The reaction rate for bisphenol A removal is ∼25 times higher than that of the CuAlO 2 . According to the characterization, Cu(II) generation on the surface of CuAlO 2 during the surface growth process results in the marked decrease of the surface oxygen vacancies and the formation of the C-O-Cu bridges between CN and Cu(II)-CuAlO 2 in the catalyst. The electron paramagnetic resonance (EPR) analysis and density functional theory (DFT) calculations demonstrate that the dual reaction centers are produced around the Cu and C sites due to the cation-π interactions through the C-O-Cu bridges in CN-Cu(II)-CuAlO 2 . During the Fenton-like reactions, the electron-rich center around Cu is responsible for the efficient reduction of H 2 O 2 to • OH, and the electron-poor center around C captures electrons from H 2 O 2 or pollutants and diverts them to the electron-rich area via the C-O-Cu bridge. Thus, the catalyst exhibits excellent catalytic performance for the refractory pollutant degradation. This study can deepen our understanding on the enhanced Fenton reactivity for water purification through functionalizing with organic solid-phase ligands on the catalyst surface.

Metal-containing Fenton catalysts have been widely investigated. Here, we report for the first time a highly effective stable metal-free Fenton-like catalyst with dual reaction centers consisting of 4-phenoxyphenol-functionalized reduced graphene oxide nanosheets (POP-rGO NSs) prepared through surface complexation and copolymerization. Experimental and theoretical studies verified that dual reaction centers are formed on the C-O-C bridge of POP-rGO NSs. The electron-rich center around O is responsible for the efficient reduction of H 2 O 2 to • OH, while the electron-poor center around C captures electrons from the adsorbed pollutants and diverts them to the electron-rich area via the C-O-C bridge. By these processes, pollutants are degraded and mineralized quickly in a wide pH range, and a higher H 2 O 2 utilization efficiency is achieved. Our findings address the problems of the classical Fenton reaction and are useful for the development of efficient Fenton-like catalysts using organic polymers for different fields.

Mesoporous Cu-doped γ-Al2O3 (γ-Cu-Al2O3) was prepared via an evaporation-induced self-assembly process, in which Cu(+/2+) was co-incorporated into mesoporous γ-Al2O3 by chemical bonding of Al-O-Cu. The catalyst was found to be highly effective and stable for the degradation and mineralization of aromatic pollutants, as demonstrated with bisphenol A, 2,4-dichlorophenoxyacetic acid, ibuprofen, diphenhydramine, and phenytoin in the presence of H2O2 under neutral pH conditions. In addition, the high utilization efficiency of H2O2 was maintained at approximately 90% prior to the disappearance of the initial aromatic pollutants. On the basis of all of the characterization results, the pollutant degradation processes predominantly occurred on the surface of the catalyst due to the formation of σ-Cu-ligand complexes between the phenolic OH group and the surface Cu. In the reaction system, in addition to the unselective oxidation by (•)OH, H2O2 directly attacked the σ-Cu(2+)-complexes aromatic ring with the phenolic OH group, which resulted in the formation of (•)OH and HO-adduct radicals that were oxidized to hydroxylation products by reduction of Cu(2+) in the σ-Cu(2+)-complexes to Cu(+). The process prevented Cu(2+) from oxidizing H2O2 to form HO2(•)/O2(•-) or O2, and enhanced the Cu(+)/Cu(2+) cycle, the formation of (•)OH, and the utilization efficiency of H2O2. Therefore, an extraordinarily high degradation and mineralization of the aromatic pollutants was observed.