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Abstract Actualizing efficient and sustainable environmental catalysis is essential in global water pollution control. The single-atom Fenton-like process, as a promising technique, suffers from reducing potential environmental impacts of single-atom catalysts (SACs) synthesis and modulating functionalized species beyond the first coordination shell. Herein, we devised a high-performance SAC possessing impressive Fenton-like reactivity and extended stability by constructing abundant intrinsic topological defects within carbon planes anchored with Fe−N4 sites. Coupling atomic Fe−N4 moieties and adjacent intrinsic defects provides potent synergistic interaction. Density functional theory calculations reveal that the intrinsic defects optimize the d-band electronic structure of neighboring Fe centers through long-range interactions, consequently boosting the intrinsic activity of Fe−N4 sites. Life cycle assessment and long-term steady operation at the device level indicate promising industrial-scale treatment capability for actual wastewater. This work emphasizes the feasibility of synergistic defect engineering for refining single-atom Fenton-like chemistry and inspires rational materials design toward sustainable environmental remediation.

Single-atom catalysts (SACs) have attracted extensive attention due to their unique catalytic properties and wide range of applications. Advanced characterization techniques, such as energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, and X-ray absorption fine-structure spectroscopy, have been used to investigate the elemental compositions, structural morphologies, and chemical bonding states of SACs in detail, aiming at unraveling the catalytic mechanism. Meanwhile, theoretical calculations, such as quantum chemical calculations and kinetic simulations, were used to predict the catalytic reaction pathways, active sites, and reaction kinetic behaviors of SACs, providing theoretical guidance for the design and optimization of SACs. This review overviews advanced characterization techniques and theoretical calculations for SACs in Fenton-like chemistry. Moreover, this work highlights the importance of advanced characterization techniques and theoretical calculations in the study of SACs and provides perspectives on the potential applications of SACs in the field of environmental remediation and the challenges of practical engineering.

Fe/Cu bimetallic catalysts have a synergistic effect that can effectively enhance catalytic activity, so Fe/Cu bimetallic catalysts have been extensively studied. However, the efficacy and mechanisms of Fe/Cu bimetallic catalysts’ peroxidation activation have rarely been explored. In this study, Fe/Cu bimetallic materials were fabricated to catalyze different oxidizing agents, including peroxymonosulfate (PMS), peroxydisulfate (PDS), peroxyacetic acid (PAA), and hydrogen peroxide (H2O2), for the degradation of sulfamethoxazole (SMX). The Fe/Cu/oxidant systems exhibited an excellent degradation efficiency of sulfamethoxazole (SMX). In the Fe/Cu/PMS, Fe/Cu/PDS, and Fe/Cu/PAA systems, the main reactive oxygen species (ROS) responsible for SMX degradation were hydroxyl radical (•OH) and singlet oxygen (1O2), while the main ROS was only •OH in the H2O2 system. The differences in the surface structure of the materials before and after oxidation were examined, revealing the presence of a large amount of flocculent material on the surface of the oxidized PMS material. Anion experiments and actual body experiments also revealed that the PMS system had a strong anti-interference ability. Finally, a comprehensive comparison concluded that the PMS system was the optimal system among the four oxidation systems. Overall, this work revealed that the PMS oxidant has a better catalytic degradation of SMX compared to other oxidizers for Fe/Cu, that PMS generates more ROS, and that the PMS system has a stronger resistance to interference.

In advanced oxidation processes with metal-containing catalysts, metal dissolution usually leads to reduced efficiency and biotoxicity. Therefore, it is very important to find efficient non-metallic materials. In this work, a metal-free mesoporous tubular g-C3N4 was fabricated using melamine and urea mixed according to the mass ratios of 1:12 (TPCN12) by a facile one-step thermal polymerization method. Mesoporous tubular TPCN12 was proved to be successfully synthesized by scanning electron microscope (SEM) and X-ray diffraction (XRD). Then the degradation of carbamazepine (CBZ) by activating peroxymonosulfate (PMS) of TPCN12 under visible light was investigated. It was found that degradation rate constant of CBZ in TPCN12/Vis/PMS system (0.0939 min−1) exhibited great superiority over that in TPCN12/Vis system (0.0149 min−1) and in TPCN12/PMS system, which indicated TPCN12, Vis and PMS had a synergistic effect. The dominant role of the electron transfer and the primary contribution of the holes (h+) and •O2− reactive species were revealed in TPCN12/Vis/ PMS system. Furthermore, the system showed sufficient advantages over a wide pH range and high resistance to inorganic anions. In general, the TPCN12/Vis/PMS system was capable of high stability and recyclability. This metal-free mesoporous tubular catalyst was proposed to achieve efficient and green elimination of pharmaceutical organic pollutants.

Developing a green, low-carbon, and circular economic system is the key to achieving carbon neutrality. This study investigated the organics removal efficiency in a three-dimensional electrode reactor (3DER) constructed from repurposed industrial solid waste, i.e., Mn-loaded steel slag, as the catalytic particle electrodes (CPE). The CPE, a micron-grade material consisting primarily of transition metals, including Fe and Mn, exhibited excellent electric conductivity, catalytic ability, and recyclability. High rhodamine B (RhB) removal efficiency in the 3DER was observed through a physical modelling experiment. The optimal operating condition was determined through a single-factor experiment in which 5.0 g·L−1 CPE and 3 mM peroxymonosulfate (PMS) were added to a 200 mL solution of 10 mM RhB under a current intensity of 0.5 A and a 1.5 to 2.0 cm distance between the 2D electrodes. When the initial pH value of the simulated solution was 3 to 9, the RhB removal rate exceeded 96% after 20 min reaction. In addition, the main reactive oxidation species in the 3DER were determined. The results illustrated that HO• and SO4•− both existed, but that the contribution of SO4•− to RhB removal was much lower than that of HO• in the 3DER. In summary, this research provides information on the potential of the 3DER for removing refractory organics from water.

The effect of peroxymonosulfate (PMS) activated by nanocrystalline CuCo2O4 (NPS) on removal of atrazine (ATZ) was studied. First, the main experimental parameters were studied, including CuCo2O4 dose, PMS dose, initial pH value, and co-existing ion. The removal of ATZ (>99%) was attained under the optimal conditions (i.e., 150 mg/L CuCo2O4, 0.2 mM PMS, 5 mg/L ATZ, initial pH value of 6.8, and reaction time of 30 min). However, the removal of ATZ only reached 20.9% in the PMS alone system and there was no significant ATZ removal when adding CuCo2O4 alone into the solution, proving the good performance of the CuCo2O4/PMS system. Furthermore, reusability of CuCo2O4 was tested through five consecutive runs. To confirm which main active radicals were responsible in the system, two radical quenching experiments were carried out and electron paramagnetic resonance (EPR) was tested. In addition, the characterization of fresh and reacted CuCo2O4 NPs was tested by SEM, TEM, EDS, XRD, and XPS. Subsequently, based on the characterization of CuCo2O4 NPs and identification of radicals, ≡Cu2+/ ≡ Cu+ and ≡Co3+/ ≡ Co2+ were considered to be the main catalytic species, while the synergistic effect of Cu and Co played a crucial role. Finally, the degradation pathway of ATZ was proposed. HIGHLIGHTS Nanoparticles CuCo2O4 was fabricated as peroxymonosulfate activator.; ATZ could be effectively degraded by CuCo2O4/PMS system.; Five degradation pathways of ATZ were proposed.; CuCo2O4 has excellent reusability.;

Herein, a highly efficient electro-peroxone (E-peroxone) process with graphite felt as ozone diffusion electrode (ODE) was developed for the synchronous removal of pharmaceutical contaminants and inactivation of pathogenic microorganisms in real hospital wastewater. Under optimal conditions, the total organic carbon (TOC) removal rate of real hospital wastewater could reach 93.9%. Importantly, 126 pharmaceutical compounds (antibiotics, antivirals, analgesics, antiepileptics, hormones, and others) were determined in hospital wastewater by using ultra performance liquid chromatography combined with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS/MS). 110 pharmaceutical compounds could be efficiently degraded in E-peroxone system. Concurrently, the microbial community analysis through high-throughput sequencing showed that E-peroxone process exhibited an excellent disinfection effect in real hospital wastewater. Escherichia coli as a bacterial indicator could be completely inactivated in E-peroxone process·H2O2 and hydroxyl radical (·OH) were found in E-peroxone system based on the results of chemical probe experiments and electron paramagnetic resonance (EPR) analysis. The in-situ generation of H2O2 from cathodic oxygen reduction in ODE can react with ozone to produce ·OH, and realize high efficiencies for the elimination of pharmaceutical and sterilization. This work established a green and effective way without extra addition of chemical reagents for high-efficiency treatment of real hospital wastewater.