ABSTRACT Sustained and selective generation of singlet oxygen ( 1 O 2 ) in Fenton‐like catalytic systems is highly desirable for diverse applications, from freshwater resource management to green chemical synthesis. Despite advances in advanced oxidation processes, there remains a lack of generalizable methods that reliably modulate 1 O 2 selectivity. Here, we propose a descriptor‐assisted coordination modulation strategy, in which machine‐learning analysis identifies the d‐band center as an important electronic descriptor associated with 1 O 2 selectivity. Through N‐coordination modulation, the CoN 5 catalyst exhibited near‐complete 1 O 2 selectivity among the quantified reactive oxygen species (ROS) with a steady‐state concentration of 394 µM, outperforming recent reports. As an internal‐circulation pre‐oxidation module, the CoN 5 /peroxymonosulfate (CoN 5 /PMS) system continuously raised wastewater biochemical oxygen demand/chemical oxygen demand (BOD/COD) to above 0.5 over 192 h, increased bioavailable dissolved organic matter (DOM), and showed high microbiome compatibility, evidenced by reduced Vibrio fischeri inhibition and microbial diversity ordination clustering near the background with greater shared‐taxa overlap. This system also enabled selective thioanisole oxidation, achieving 90.6% conversion and 99.5% selectivity, with green synthesis potential demonstrated in a three‐chamber continuous single‐pass reactor. These results establish a generalizable coordination principle for steering ROS pathways and provide a deployable, low‐ecological‐risk route for both mixed wastewater treatment and green chemical synthesis.

Enantioselective synthesis of five-membered heterocycles bearing chiral tetrasubstituted allylic alcohols remains challenging due to severe steric hindrance and strict regio- and enantio-control demands. Herein, we report an efficient, highly enantioselective Ni(0)-catalyzed cascade syn-arylative cyclization of hetero-1,6-alkynones with arylboronic acids, enabling direct access to chiral pyrrolidines and tetrahydrofurans with chiral quaternary carbon stereocenters. Using Ni(cod)(2)/(S)-BIDIME, tert-butanol, and LiOMe, 35 products were obtained in up to 98% yield and >99 : 1 er. Gram-scale synthesis proceeded without erosion of reactivity or enantioselectivity. Mechanistic studies and DFT calculations revealed that the cyclization forming the Ni(II) metallacycle is the enantio-determining step. This work provides a practical strategy for the synthesis of chiral five-membered heterocycles and valuable mechanistic insights for the design of asymmetric catalysts.

Currently, catalytic recycling of polyethylene (PE) into high-value chemicals using solar energy often faces poor product selectivity and low efficiency. This is mainly due to the difficulty in effectively controlling the intermediates during PE photoreforming and the long-standing challenge of inefficient charge dynamics. Here, we present a solar-driven photothermal catalytic approach for the selective conversion of PE waste into propionic acid and hydrogen under ambient conditions. Atomically dispersed Ni sites supported on CeO 2 (Ni SA /CeO 2 ) achieve a propionic acid yield of 331 μmol h –1 with 94.8% selectivity in the photothermal reaction. This performance is 1.6 times higher than that of catalysts supported by Ni clusters (Ni NP /CeO 2 ). Additionally, Ni SA /CeO 2 exhibits a hydrogen yield of 0.23 mmol h –1 with stable long-term performance. Mechanistic studies reveal that single Ni atoms form linear coordination with oxygen atoms in CeO 2 , introducing unoccupied mid-gap states that effectively capture hot electrons and enhance the photothermal effect through local hotspot formation. In contrast, Ni clusters suffer from inefficient heat accumulation due to multistep phonon scattering. Furthermore, site isolation of Ni single atoms spatially separates the reaction intermediates and suppresses dimerization of the key intermediate COOHCH 2 CH 2 *, thereby greatly improving the selectivity for propionic acid. In contrast, closely packed Ni cluster sites promote intermediate coupling and the formation of undesirable byproducts, reducing selectivity. This work provides mechanistic insights into the advantages of atomic-scale catalyst design for selective chemical transformations.

Tetracycline (TC) as one kind of characteristic antibiotic has caused serious environment problems. In this study, a Mo(VI)-cluster containing iron-based metal-organic framework (MOF), [Fe(Mo4O13)(TPT)(2)] (FeMo-TPT, TPT = 2,4,6-tri(4-pyridyl)-1,3,5-triazine), was synthesized and applied in the photocatalytic degradation of TC. The existence of Fe(II) cations and Mo(VI)-clusters could enhance the visible light harvesting through reducing the band gap energy. The synergistic effect in the structure enhances the photodegradation of TC. Photochemical characterizations proved FeMo-TPT has strong ability of photoinduced electron and hole separation. In the confined space, the ordered electrons transport occurred between each component. Consequently, FeMo-TPT exists a 98.01 % degradation rate with oxygen as an oxidant under mild condition. A possible degradation way of TC was investigated by mass spectrometry. And the reactive oxygen species (ROS) capture tests and EPR results show that O-1(2) and O-2(center dot-) play the important role in TC degradation process. This work provides an efficient photocatalyst for water environment treatment under mild condition.

In recent years, antibiotics have been widely used in multiple fields such as agriculture, forestry, animal husbandry as well as human health due to their high efficiency and low price in treating bacterial infections. However, the misuse of antibiotics has posed a serious threat to both ecological environment and human health, resulting in the antibiotic contamination as a global issue. Therefore, the development of novel materials and technologies to remove antibiotics from water has become a research frontier and hotspot. Meanwhile, mesoporous silica materials have been gradually used in the removal of antibiotics via adsorption and degradation due to their controllable structure, tunable pore size as well as diverse sources. This mini review focuses on the research progress of mesoporous silica in removing antibiotics from aquatic environments. The main types and controllable synthesis procedures of mesoporous silica is introduced first, followed by their application in antibiotics removal via both adsorption and catalytic degradation. Furthermore, it proposes the future directions of this field, providing insights for the use of mesoporous silica materials in water pollution control.

Biomass-derived carbonaceous materials exhibit fascinating potentials in nonradical oxidation of micropollutants (MPs) by activating persulfate and their performances mainly rest on graphitic N. However, the simultaneously derived N vacancy received little attention. Herein, a graphene-like material rich in N vacancy was synthesized from coffee residues. It showed excellent removal efficiency (95 %) and degradation kinetics (0.21 min(-1)) in abating tetracycline antibiotics from secondary effluent and significant biotoxicity was diminished. Solid nonradical oxidation consisting of electron transfer (89 %) and singlet oxygen (O-1(2)) oxidation (11 %) was determined. By tracking O-1(2) source and electron flow, ketone group appeared at N vacancy was found as the critical site to grab electrons from peroxydisulfate (PDS) with production of O-1(2). Then the electrons were transferred to graphitic N driven by the microelectric field between them. This work notices the function of vacancies in biomass resources for high-efficient removal of MPs from real water matrix.

Plastic waste pollution presents a critical environmental challenge, with polyethylene terephthalate (PET) among the most prevalent and persistent forms of plastic waste. This study develops a sustainable electrocatalytic strategy to upcycle PET‐derived ethylene glycol (EG) into high‐value glycolic acid (GA) using Ni─Fe dual single‐atom catalysts (Ni 1 ─Fe 1 ─N─C DSACs). By optimizing the binding energies of *EG and *OH through dual‐site synergy, the catalysts achieve a Faradaic efficiency of 96.1% and selectivity above 90% for GA production. Mechanistic insights reveal that oxygen‐affine Ni atoms facilitate *OH generation, enhancing EG oxidation while preventing over‐oxidation. The technology is demonstrated in a membrane electrode assembly (MEA) flow electrolyzer, achieving stable electrolysis for over 100 h with a Faradaic efficiency exceeding 85%. A life cycle assessment (LCA) confirms that electrocatalytic reforming outperforms mechanical recycling and incineration across multiple environmental and economic indicators, significantly reducing carbon emissions, enhancing resource efficiency, and ensuring greater process stability. These findings highlight the potential of electrocatalytic PET upcycling as a scalable and environmentally sustainable solution for addressing plastic pollution and advancing circular economy goals.

The sodium extraction/insertion in layered transition-metal oxide (TMO) cathode materials are typically accompanied by slab sliding and lattice changes, leading to microstructure destruction and capacity decay. Herein, negative lattice expansion is observed in an O3 type Ni-based layered cathode of Na 0.9 Ni 0.32 Zn 0.08 Fe 0.1 Mn 0.3 Ti 0.2 O 2 upon Na + extraction. It is attributed to the weak Zn 2+ −O 2− orbital hybridization and increased electron density of the surrounding oxygen for reinforced interlayer O−O repulsive force. This enables gliding of TMO slabs for the intergrowth phase transition of P3→OP2 to alleviate lattice strain with moderate lattice shrinkage, which exhibits general interslab spacings and volume changes as low as 2.4 % and 1.9 %, respectively. The strong Ti−O bonds accommodate the internal distortion of TMO 6 octahedra due to the flexibility of TiO 6 octahedra during cycling. These endow a high specific capacity of 144.9 mAh g −1 and excellent cycling performance of pouch-type sodium-ion batteries with 93 % capacity retention after 3600 cycles.

Layered transition-metal (TM) oxide cathodes have attracted growing attention in sodium-ion batteries (SIBs). However, their practical implementation is plagued by Jahn-Teller distortion and irreversible cation migration, leading to severe voltage decay and structure instability. Herein, O3-Na0.898K0.058Ni0.396Fe0.098Mn0.396Ti0.092O2 (KT-NFM) is reported as an ultrastable cathode material via multisite substitution with rigid KO6 pillars and flexible TiO6 octahedra. The K pillars induce contracted TMO2 slabs and their strong Coulombic repulsion to inhibit Ni/Fe migration; and Ti incorporation reinforces the hybridization of Ni(3deg*)-O(2p) to mitigate the undesired O3-O'3 phase transition. These enable the reversible redox of Ni2+↔Ni3 . 20+ and Fe3+↔Fe3.69+ for 138.6 mAh g-1 and ultrastable cycles with >90% capacity retention after 2000 cycles in a pouch cell of KT-NFM||hard carbon. This will provide insights into the design of ultrastable layered cathode materials of sodium-ion batteries and beyond.

A novel microporous iron-based MIL-101@MIL-53 Z-scheme heterojunction photocatalyst was synthesized via a one-pot solvothermal strategy. Composition, structure, morphology and optical properties of the prepared photocatalyst were characterized using XRD, SEM, FT-IR, XPS and UV-vis DRS. The formation mechanism of the iron-based MIL-101@MIL-53 Z-scheme heterojunction was proposed to be attributed to the gradual transformation from MIL-101 to MIL-53. The in situ formation of an iron-based MIL-101@MIL-53 Z-scheme heterojunction facilitated the electron transfer from MIL-53 to MIL-101. Therefore, the separation of photogenerated charge carriers was enhanced. The removal efficiency of 300 mg L-1 tetracycline hydrochloride reached 99.6% in 90 min under simulated solar light irradiation. Radical capturing experiments showed that (center dot)O2- was the main active substance for the degradation of tetracycline hydrochloride. This work provided strategies for development and application of iron-based MIL-101@MIL-53 Z-scheme heterojunction and efficient treatment of wastewater with a high tetracycline hydrochloride concentration. In situ formation of an iron-based MIL-101@MIL-53 Z-scheme heterojunction promoted the separation of photogenerated carriers. Superoxide radical was the main active substance for tetracycline degradation.

The emerging contaminants in the environment pose a threat to ecological security and human health. At present, traditional technologies are difficult to detect and remove existing trace emerging contaminants in water bodies. Therefore, efficient removal of low concentration emerging contaminants is a key issue in ensuring water safety. As an emerging technology, molecular imprinting technology (MIT) can synthesize polymers with specific recognition ability for target pollutants, providing a new approach for efficient removal of emerging contaminants. It is worth noting that combining MIT with traditional catalysts is an effective method to improve detection limits and removal efficiency. This review mainly introduced the research progress of using MIT to detect pollutants in various sensors and using advanced oxidation technology to remove pollutants in recent years, focusing on the preparation and application of MIT-based photocatalysts, electrocatalysts, and Fenton-like catalysts. In addition, possible interactions between the target analyte and MIT were discussed, as well as the reusability and stability of imprinted catalysts in water treatment, and their potential ecological toxicity risks were analyzed. Finally, the challenges of MIT based pollutant mitigation and the application prospects of molecular imprinting technology in environmental analysis were elaborated from multiple perspectives.

Hydrogen peroxide (H2O2) is an important green oxidant with a wide range of applications in wastewater treatment, pulp bleaching and chemical synthesis. In recent years, two -electron oxygen reduction reaction (2e-ORR) is expected to be a greener and safer alternative to the more energy -intensive and also carcinogenic anthraquinone process. Among the various electrocatalysts for 2e-ORR, two-dimensional nanomaterials have special advantages in the electrosynthesis of H2O2 due to their large specific surface area, abundant basal and edge sites, and tunable atomic structure. This review article summarizes the synthesis methods, and the strategies and mechanisms for enhancing 2e-ORR properties of 2D materials. Practical problems and serious challenges faced by 2D nanomaterials in the synthesis and 2eORR applications are elaborated. The aim of this review is to provide researchers with an understanding of 2D nanomaterials in electrocatalytic applications and to promote the further development of novel 2D nanoelectrocatalytic materials. (c) 2024 Elsevier Ltd. All rights reserved.

Layered manganese-based oxides are promising cathode materials for potassium-ion batteries (PIBs) owing to the abundant K resources. However, their energy density is limited to the accessible redox centers. Herein, P'2-type K0.51Mn0.93Mn□0.07O2 (Mn□ = Mn vacancy) is synthesized to activate anionic redox reactions (ARRs) by introducing native Mn vacancies into the transition-metal slabs. The vacant Mn sites facilitate the formation of non-bonding O 2p orbitals to trigger ARRs, owing to their high orbital energy close to the Fermi level, and provide additional capacity. The presence of ARRs suppresses phase transition and results in formation of O-O dimers for stable oxygen networks to mitigate oxygen loss. High specific capacity of 116 mAh g-1 with long cycle stability can be obtained based on the successive redox of Mn3.75+/Mn3.88+ and O2-/On- (n < 2). This work provides a new pathway to activate ARRs with vacancies for high specific capacities and stable cycling for PIBs.

As a kind of novel and persistent environmental pollutants, antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) have been frequently detected in different aquatic environment, posing potential risks to public health and ecosystems, resulting in a biosecurity issue that cannot be ignored. Therefore, in order to control the spread of antibiotic resistance in the environment, advanced oxidation technology (such as Fenton-like, photocatalysis, electrocatalysis) has become an effective weapon for inactivating and eliminating ARB and ARGs. However, in the process of advanced oxidation technology, studying and regulating catalytic active sites at the molecular level and studying the adsorption and surface oxidation reactions between catalysts and ARGs can achieve in-depth exploration of the mechanism of ARGs removal. This review systematically reveals the catalytic sites and related mechanisms of catalytic antagonistic genes in different advanced oxidation processes (AOPs) systems. We also summarize the removal mechanism of ARGs and how to reduce the spread of ARGs in the environment through combining a variety of characterization methods. Importantly, the potential of various catalysts for removing ARGs in practical applications has also been recognized, providing a promising approach for the deep purification of wastewater treatment plants.

The extensive accumulation of plastic waste has given rise to severe environmental pollution issues. Contemporary conventional recycling methods, such as incineration and landfilling, contribute significantly to pollutant emissions and carbon footprints, against the principles of sustainable development. Leveraging renewable solar energy to transform plastics into high-value chemicals and green fuels offers a more promising and sustainable approach to managing plastic waste resources. This comprehensive review centers on the recent advancements in plastic photoreforming, categorizing them based on the types of end products. Particular emphasis is placed on the evolving research landscape surrounding the conversion of plastics into high-value chemicals through photoreforming, as well as the economic considerations for large-scale photoreforming production. The analysis conducted here reveals key pathways and emerging trends that are poised to shape the trajectory of enhanced photoconversion, ultimately influencing the realization of a carbon-neutral future.

Water pollution by dyes is one of the biggest environmental problems. Adsorption technology has been widely used in wastewater treatment. In this work, high-entropy concept is used to design surface defective hydroxides realizing the rapid removal of dyes from water. Multi-element hydroxides (MEHs) containing three (CoMnNi, MEH-Ternary), four (CoMnNiZn, MEH-Quaternary), and five (CoMnNiZnFe, MEH-Quinary) metal elements are successfully synthesized through a polyol process. These as-synthesized MEHs are composed of nanosheets with a brucite-like structure. Along with the increase in compositional complexity (i.e., configurational entropy), the thickness of the nanosheets in these MEHs decreases, while the degree of surface defects increase. These surface defects are probably the active sites for anionic dyes adsorption, suggesting rapid adsorption kinetics with shortened diffusion path length. For MEH-Quinary in 0.2 mM Congo red (CR) and MEH-Ternary in 0.4 mM methyl orange (MO) aqueous solutions, respectively, high removal efficiency > 99.0% is achieved in the first 30 s. Their pseudo-second-order rate constants are two orders of magnitude higher than that of activated carbon and hydrotalcite. MEH-Quinary has maximum CR and MO adsorption quantity of 546.4 and 404.9 mg g-1, respectively, by Langmuir model. The MEH-Quinary is also a potential electrocatalyst for oxygen evolution reaction.

The low exposure of active sites and the slow electron transfer rate still restrict the wide application of the photoFenton system of Fe-based photocatalyst in practical water treatment. Herein, we prepared a hollow Fe-doped In2O3 nanotube (h-Fe-In2O3) catalyst for activating hydrogen peroxide (H2O2) to remove tetracycline (TC) and antibiotic resistant bacteria (ARB). Incorporation of Fe could shorten the band gap and increase the absorption capacity of visible light. Meanwhile, the increase of electron density at the Fermi level promotes the interfacial electron transport. The large specific surface area of the tubular structure exposes more Fe active site and the FeO-In site reduces the energy barrier of H2O2 activation, resulting in more and faster formation of hydroxyl radicals (center dot OH). After continuous operation for 600 min, the h-Fe-In2O3 reactor still can remove 85% TC and about 3.5 log ARB in secondary effluent, showing good stability and durability for practical wastewater treatment.

In this work, we presented the preparation of magnetic carbon nanotubes (MCNTs) functionalized with molecularly imprinted polymers (MIPs) for effective removal of aristolochic acid I (AAI) in traditional Chinese medicine (TCM). MCNTs@AAI-MIPs was obtained via a facile and environmental friendly sol-gel process. Firstly, MCNTs were synthesized by a solvothermal method. Then, the template molecules were self-assembled with the functional monomer phenyltrimethoxysilane (PTMOS) in the presence of ethanol and water. Finally, AAI-MIPs film was coated on the MCNTs to obtain product MCNTs@AAI-MIPs using tetraethyl-orthosilicate (TEOS) as cross-linker. The morphology and structure of prepared MIPs were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray diffraction (XRD), nitrogen gas adsorption and vibrating sample magnetometer (VSM). The adsorption properties were demonstrated by kinetic, isothermal and selective adsorption experiments. The results showed that the imprinted nanocomposites exhibited fast separation rate (10 s), high adsorption capacity (18.54 μg∙mg-1), short kinetic equilibrium time (15 min), and good selectivity to template molecule with imprinting factor (IF) of 3.17. A regression equation (y=57294x-4734.1) with good linearity was obtained in the concentration range of 0.1-200 μg∙mg-1 for AAI with a correlation coefficient (R2) of 0.9998. The limit of detection (LOD, S/N=3) was 0.034 μg∙mg-1. Moreover, high recoveries ranged from 80% to 110% (RSD=3.27%-8.16%) were received in spiked TCM samples. The results suggested that the proposed MCNTs@AAI-MIPs could efficiently and specifically capture AAI from an actual complex TCM samples.