Electron-rich catalytic surfaces have been widely employed in the electrochemical reduction of nitric oxide (eNORR) for ammonia electrosynthesis. However, their influence on the reaction mechanism, particularly solvent effects, remains poorly understood. In this study, we developed an electron-rich core/shell catalyst by encapsulating tungsten trioxide with a graphene layer (WO3-x@GR) to investigate its role in modulating solvent effects. This catalyst achieved an ammonia yield of 4365 μmol mg-1 h-1 and a faradaic efficiency (FE) of 91.1% at -0.54 V vs. RHE over 100 h of continuous operation, surpassing most recently reported catalysts. Electronic structure analyses demonstrated that oxygen vacancies (Ov) in the WO3 core facilitated interfacial electron transfer, thereby generating electron-rich active sites within the graphene (GR) shell. Moreover, ab initio molecular dynamics (AIMD) simulations indicated that water molecules preferentially adopted an H-down orientation at these active sites, weakening nitric oxide (NO) adsorption through hydrogen bonding while enhancing NOH adsorption via hydrogen-atom repulsion. This reorientation lowered the energy barrier of the potential rate-determining step (*NO → *NOH) from 2.18 eV to 1.16 eV, thereby significantly enhancing eNORR activity. Collectively, this study provides new molecular-level insights into solvent effects in eNORR and offers guidance for the rational design of high-performance electrocatalysts.

Despite maximal atomic efficiency, single-atom catalysts (SACs) are constrained by linear scaling relationships in electrocatalytic hydrodechlorination (ECHD), a process effective for antibiotic pollutant deactivation yet challenged by multi-proton /electron transfer and dilute reactant conditions. Herein, a novel cobalt (Co)-SACs consisting of single-atom Co anchored on a nitrogen-doped hollow porous carbon sphere (Co1/N-HCS) is fabricated, which exhibits a remarkable mass activity of 14.1 gFLO gCo -1 at -0.30 V toward florfenicol (FLO, a typical antibiotic pollutant), outperforming Co1/carbon black, Co nanoparticles/carbon black, and previously reported catalysts. Mechanistic studies reveal that the unique hollow porous architecture of N-HCS facilitates fluid dynamic enhancement and localized adsorptive enrichment of dilute FLO, while its curved surface boosts proton transfer at Co1 through localized electric field enhancement. The dual enhancements enable Co1 to break the linear scaling relationship limitations. Field tests for Co1/N-HCS in natural lake water demonstrate excellent environmental stability and matrix interference resistance. Furthermore, it could effectively deactivate dilute FLO (5 µmol L-1) while suppressing the emergence of antibiotic resistance gene, highlighting its prospect in antibiotic pollution remediation. This study introduces a paradigm-shifting support architecture to transcend the SACs performance boundary, while pioneering the application of ECHD for antibiotic pollutant remediation.

While TiO2 is a promising catalyst for electrocatalytic nitrate (NO3 - -N) reduction to NH3 (ENRR), how the crystalline phase (anatase (A) or rutile (R)) and surface oxygen vacancy (Ov ) synergize in ENRR remains ambiguous. Herein a series of nitrogen-doped TiO2 catalysts with controlled phase composition and Ov number are prepared by calcinating titanium nitride powders in an air atmosphere at specific temperatures (N-TiO2 - x , x = 450-750 degrees C). Generally, higher temperatures lead to increased R-TiO2 content but decreased Ov number. The ENRR performances of these N-TiO2 are higher than that of pure A- and R-TiO2 , and vary in volcano-like trends against both the R-TiO2 content and Ov number. Combined control experiments and theoretical simulation demonstrate that Ov s are the active sites for ENRR, but their functions differ between A-TiO2 and R-TiO2 . Specifically, the Ov s on R-TiO2 are more active in NO3 - conversion and renew more easily during reaction, while those on A-TiO2 perform better in proton adsorption. The synergy between Ov s on R-TiO2 and A-TiO2 promotes the ENRR on the phase-mixed N-TiO2 . Furthermore, as the catalyst varies from N-TiO2 -450 to -750, the overall efficacy of Ov s in proton transfer decreases due to the decreased number of Ov s on A-TiO2 , while the mean activity and renewability of them improve as a higher proportion of Ov s are distributed on R-TiO2 . The tug-of-war between the two opposing trends results in a peak ENRR performance on N-TiO2 -650 (mass activity: 22.2 mgN h-1 gcat. -1 ; NH3 -N selectivity: 98.8%; Faradaic efficiency: 79.4%). These findings offer a deeper understanding of ENRR on TiO2 , and provide new insights for the design of efficient catalysts. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Electrocatalytic hydrodechlorination (ECHD) represents a sustainable strategy for deactivating chlorinated antibiotics through hydrogenolysis of C-Cl bonds. However, its widespread application is hindered by the scarcity of cost-effective catalyst, as well as their insufficient efficiency in treating trace antibiotics. Herein, a porous superhydrophobic biochar was fabricated from rice straw via a stepwise process of thermal pyrolysis, acidic etching and chemical reduction, which demonstrates an exceptional adsorption capacity of 575.0 mg g- 1 for florfenicol (FLO) and a remarkable mass activity of 1.1 mg min- 1 g- 1 in ECHD of 20.0 mg L- 1 FLO at -0.6 V. This performance not only exceeds reported biochars produced with fewer processing steps, but also surpasses several metal-based catalysts. Our biochar was further confirmed competent in degrading more dilute FLO (2 mg L- 1) in contaminated lake water. Mechanistic investigations reveal that the outstanding ECHD performance of the biochar stems from its superhydrophobic and porous property, promoting adsorptive enrichment of trace antibiotics. In contrast, the carbon defects and oxygen-containing groups introduced during thermal pyrolysis impede electron transfer between the biochars and pollutants, due to unfavorable orbital occupancy, elevated work function and increased surface polarity within biochar. These findings emphasize the necessity of chemical reduction to remove these interfering moieties, while confirming the promise of porous and superhydrophobic biochars as sustainable catalysts for antibiotic-contaminated water remediation.

Point defect engineering is a powerful strategy to manipulate charge redistribution in biochar. Herein, dominant C-S-C point defects are successfully constructed on vacancy- and edge-rich carbon within a three-dimensional (3D) honeycomb-like hierarchical porous framework through KOH etching and S doping strategies. Benefiting from its hierarchical porosity, large specific surface area, numerous vacancies, active C-S-C sites, high defect density and favorable wettability, the as-prepared biochar catalyst delivers excellent oxygen reduction reaction (ORR) activity. SNAC-6 achieves a half-wave potential of 0.84 V and a kinetic current density of 7.67 mA cm(-2) at 0.80 V, along with outstanding durability (only 13.7% current decay after chronoamperometry tests). The flow zinc-air battery (ZAB) assembled with SNAC-6 presents great application potential, with a high specific capacity of 544 mAh gZn(-1). DFT results reveal that C-S-C point defects on vacancies and exposed edges are the primary active sites for ORR catalysis. Meanwhile, defective carbon and N dopants synergistically modulate the electronic structure, further improving catalytic performance. This work deepens the understanding of point defect effects and offers a feasible route to rationally tailor the electronic and porous structures of biochar electrocatalysts.

Electrocatalytic reduction of nitrate (NO 3 − , NO3RR) on single-atom copper catalysts (Cu-SACs) offers a sustainable approach to ammonia (NH 3 ) synthesis using NO 3 − pollutants as feedstocks. Nevertheless, this process suffers from inferior NO3RR kinetics and nitrite accumulation owing to the linear scaling relation limitations for SACs. To break these limitations, a single-atom Cu-bearing tungsten oxide catalyst (Cu 1 /WO 3 ) was developed, which mediated a unique dual-driven NO3RR process. Specifically, WO 3 dissociated water molecules and supplied the Cu 1 site with ample protons, whereas the Cu 1 site in an electron-deficient state converted NO 3 − to NH 3 efficiently. The Cu 1 /WO 3 delivered an impressive NH 3 production rate of 1274.4 mg N h −1 g Cu −1 , a NH 3 selectivity of 99.2%, and a faradaic efficiency of 93.7% at −0.60 V, surpassing most reported catalysts. Furthermore, an integrated continuous-flow system consisting of a NO3RR cell and a vacuum-driven membrane separator was developed for NH 3 synthesis from nitrate-contaminated water. Fed with the Yangtze River water containing ∼22.5 mg L −1 of NO 3 − -N, this system realized an NH 3 production rate of 325.9 mg N h −1 g Cu −1 and a collection efficiency of 98.3% at energy consumption of 17.11 kwh g N −1 . This study provides a new dual-driven concept for catalyst design and establishes a foundation for sustainable NH 3 synthesis from waste.

Layered double hydroxides (LDHs) are recognized for their potential in phosphate (P) adsorption from water, generally achieved through ionic exchange between P and the anions intercalated in LDHs. Nevertheless, their broad applications are challenged by low P selectivity owing to competitive adsorption of other anions (e.g., SO42-, CO32-, NO3-, Cl-) and the difficulty in collecting LDH powders after use. Herein, we developed a facile approach for in-situ growth of p-toluenesulfonic acid-intercalated NiAl-LDH arrays on carbon cloth (NiAl-LDH-CC), forming an integrated membrane for P adsorption. It afforded an adsorption capacity of 75.42 mg g(LDH)(-1) and demonstrated minimal drop in removal efficiency of P (similar to 3%) even in the presence of competing anions. It was regenerable in 1.0 M NaOH solution, retaining 91.9 % of its initial adsorption capacity after multiple regeneration cycles. More intriguingly, the growth of NiAl-LDH on carbon cloth facilitated their collection after use, addressing the issues of adsorbent residue in water. Mechanistic studies suggested that the enhanced selectivity for P was result from a shift in the adsorption mode from traditional ionic exchange to binding via hydrogen bonding between P and the sulfo-group of p-toluenesulfonic acid. The NiAl-LDH-CC was finally employed for adsorptive removal of P from the natural water samples in a continuous-flow mode. It could reduce the P concentration from feeding 1.00 mg/L to < 0.24 mg/L under a flow velocity of 100 L h(-1) m(-2).

The electrocatalytic reduction of nitrate to ammonia (ERNA) faces significant barriers to industrial adoption, primarily due to sluggish reaction kinetics. Here, we demonstrate a CO2 absorption (CO2(abs)) assisted ERNA system through electrolyte engineering that simultaneously enhances catalytic activity and suppresses competing reactions. First, CO2(abs) neutralizes OH- during ERNA, promoting the ionization of H2O to generate more protons (H+) for the reaction. Second, CO2(abs) enhances the adsorption strength of intermediates through intermolecular forces, thereby inhibiting the hydrogen evolution reaction (HER). This electrolyte engineering approach leads to a 65 % improvement in selectivity and a 76 % increase in faradaic efficiency (FE) for the CoO/ Cu electrode. It also facilitates enhanced selectivity and FE for other common electrodes, such as Cu foam, Cu foam/Co3O4, and Fe plates, in ERNA. In coal chemical wastewater treatment, the system achieves a yield of 23.4 mg cm- 2 h- 1 of NH4HCO3 at an energy consumption of 19.3 kWh kg- 1 (a more than 40 % reduction in energy use), outperforming conventional methods. This waste-to-resource approach simultaneously addresses nitrate remediation and CO2 utilization, offering a sustainable pathway for nitrogen and carbon recovery.

Herein, a recrystallization approach was used to produce anhydrous sodium sulfate (ASS) microparticles, which are highly efficient and reusable for separating surfactant-stabilized water from water-in-oil emulsions. The ASS microparticles exhibit distinct morphologies and crystal structures. Remarkably, 0.1 g of ASS170 enables the separation of 10 mL of emulsion (water content: 0.1 g) with a high separation efficiency of 98.63%. A stepwise separation mechanism, including demulsification and water immobilization in the crystal lattice of ASS, is proposed. The superhydrophilicity of ASS particles enables tiny water droplets to aggregate and merge into larger droplets on their surfaces. This process facilitates the phase transition from ASS to sodium sulfate decahydrate (SSD), during which water molecules are immobilized in the expanded crystal lattice of ASS. SSD particles can be collected to regenerate ASS, retaining the high performance of the original ASS. This unique renewable feature reduces the cost of utilizing ASS and simultaneously prevents secondary pollution. Further economic evaluation reveals that it only costs 66.51 USD/m3 to purify emulsion with a water content of 10 g/L, significantly lower than previously reported materials. Coupled with a facile and environmentally friendly preparation strategy, this method shows great application potential for water-in-oil emulsion separation and oil purification.

BACKGROUND CONTEXT: Upper cervical complex fractures are associated with high rates of neurological damage and mortality. The Dickman's classification is widely used in the diagnosis of upper cervical complex fractures. However, it falls short of covering the full spectrum of complex fractures. This limitation hinders effective diagnosis and treatment of these injuries. PURPOSE: To address the diagnostic gap in upper cervical complex fractures, the study introduces a novel classification system for these injuries, assessing its reliability and usability. STUDY DESIGN: Proposal of a new classification system for upper cervical complex fractures. PATIENT SAMPLE: The study comprised the clinical data of 242 patients with upper cervical complex fractures, including 32 patients treated at our hospital, along with an additional 210 cases from the literature. OUTCOME MEASURES: The interobserver and intra-observer reliability (kappa coefficient, K ) of this classification system were investigated by 3 spine surgeons. The 3 researchers independently reevaluated the upper cervical complex fracture classification system 3 months later. METHODS: The proposed classification categorizes upper cervical complex fractures into 3 main types: Type I combines odontoid and Hangman's fractures into 2 subtypes; Type II merges C1 with odontoid/Hangman's fractures into 3 subtypes; and Type III encompasses a combination of C1, odontoid, and Hangman's fractures, divided into 2 subtypes. Meanwhile, a questionnaire was administered in 15 assessors to evaluate the system's ease of use and clinical applicability. RESULTS: A total of 45 cases (18.6%) unclassifiable by Dickman's classification were successfully categorized using our system. The mean K value of inter-observer reliability was 0.783, indicating substantial reliability. The mean K value of intraobserver reliability was 0.862, indicating almost perfect reliability. Meanwhile, thirteen assessors (87.7%) stated that the classification system is easy to remember, easy to apply, and they expressed intentions to apply it in clinical practice in the future. CONCLUSIONS: This system not only offers high confidence and reproducibility but also serves as a precise guide for clinicians in formulating treatment plans. Future prospective applications are warranted to further evaluate this classification system. (c) 2024 Elsevier Inc. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Electrocatalytic hydrodechlorination (EHDC) is an effective technology for the deactivation of antibiotics in environmental matrices. Although carbon-based catalysts exhibit good durability in EHDC, their catalytic performance is limited by suboptimal electronic structures. In this study, a core/shell catalyst consisting of a defective tungsten oxide core and a graphitic carbon shell (WO3@GP) was fabricated to enhance the catalytic activity of carbon materials in EHDC. WO3@GP achieved a mass activity of 80 gFLO h- 1 g- 1 (533 gFLO h- 1 m-2) and a florfenicol (FLO) removal efficiency of 99.6 % in treating 20 mg L- 1 of FLO at -1.3 V vs. Ag/AgCl, outperforming single carbon black, WO3, and previously reported carbon-based catalysts. Mechanistic studies revealed that the oxygen defects in WO3 facilitated interfacial electron transfer from the core to GP shell, elevating the Fermi level of the GP shell from -4.18 eV (pristine GP) to -3.89 eV. This upward shift reduced the energy gap toward the lowest unoccupied molecular orbital (LUMO, -2.57 eV) of the C-Cl bond in FLO, improving electronic orbital alignment and accelerating electron transfer for enhanced EHDC. Moreover, WO3@GP effectively suppressed FLO resistance gene expression in swine wastewater, reducing its relative abundance from 48.2 to 0.96. This study demonstrated that defective metal oxide core-supported carbon shell represents a viable strategy for activating carbon-based catalytic systems.

Biochar's polar oxygen-containing functional groups often limit its adsorption capacity for low-polarity antibiotics. In this study, a low-polarity porous biochar (R-PBC) was developed through KOH-assisted pyrolysis of rice straw, followed by hydrazine (N2H4) reduction. The R-PBC exhibited a 32 % higher florfenicol (FLO) adsorption capacity (242.07 mg g- 1) compared to the unreduced biochar (183.1 mg g- 1), surpassing most reported carbonbased adsorbents. The enhanced performance resulted from two key modifications: (i) A 75 % increase in specific surface area (1405.7 m2 g- 1 vs. 802.7 m2 g- 1 for PBC) through SiO2 corrosion and pore structure optimization, which facilitated superior pore filling; and (ii) the elimination of polar oxygen groups (-COOH/-OH), which strengthened it-it interactions between the biochar's aromatic structure and antibiotics. R-PBC demonstrated broad-spectrum antibiotic removal, achieving 90 % or higher efficiency for sulfamerazine (SMR), tetracycline (TC), chloramphenicol (CAP), and sulfapyridine (SPY) at a concentration of 10 mg L- 1. Adsorption followed the Langmuir isotherm and pseudo-second-order kinetics. This work provides a practical strategy for designing costeffective biochar adsorbents through polarity modulation and pore engineering.

Promoting the activation of surface or edges hydroxyl groups in layered double hydroxides (LDHs) to facilitate its conversion to hydroxyl radicals (·OH) in photocatalytic process has received wider attention in research communities. However, the pristine LDHs are unable to convert surface or edges hydroxyl groups to ·OH with the energy of visible light illumination, so it is necessary to structurally modulate them to improve their conversion of surface hydroxyl groups to ·OH under light illumination. Herein, we innovatively combined nickel-iron layered double hydroxide (NiFe-LDHs, hydroxyl groups library) with bismuth carbonate oxide ((BiO)2CO3, BOC, ·OH generator), enabling a sustained and efficient transformation of hydroxyl groups on the surface or edges of NiFe-LDHs into ·OH. Mechanism studies supported by in-situ spectroscopic analyses and theoretical simulations, showed that under the visible light illumination the hot holes generated on energy band-matched BOC can capture OH- located at the surface/edge of NiFe-LDHs nanosheets and further convert them into ·OH and efficiently promoted the oxidation of NO to NO3-. The NO removal efficiency of BOC/NiFe-LDHs composite material is about 54.5%, which was 2.23 times that of the original BOC.

Study Design.Retrospective observational study.Objective.The purpose of this study was to determine whether paraspinal muscle could influence postoperative coronal balance and its transition in degenerative lumbar scoliosis (DLS).Summary of Background Data.Although the importance of the paraspinal muscles (PSM) in sagittal alignment is well recognized, there is no information about its role in coronal balance.Methods.The study included 102 DLS patients. Evaluation of the PSM on magnetic resonance imaging were conducted at baseline. Coronal measurements included coronal balance distance (CBD), major Cobb angle, L4 coronal tilt, and L5 coronal tilt. The cohort was divided based on postoperative parameters into persistent coronal balance (PCB), worsened coronal imbalance (WCIB), recurrent coronal balance (RCB), and persistent coronal imbalance (PCIB) according to immediate postoperative and follow-up coronal balance. Multivariate logistic regression models for postoperative CIB, follow-up WCIB and follow-up RCB were utilized to identify statistically significant associations while accounting for confounders.Results.The cohort was divided into 57 with PCB, 13 with WCIB, 10 with RCB, and 22 with PCIB. The follow-up groups with CIB exhibited more severe fatty infiltration in the extensor muscle compared with the balanced groups. Specifically, the WCIB group demonstrated the most severe extensor muscle degeneration, particularly on the concave sides, and the most prominent asymmetric degeneration of the PSM among the four groups. Furthermore, patients with CIB had worse sagittal malalignment compared with those with CB at the last follow-up.Conclusions.Patients exhibiting stronger extensor muscle mass were prone to immediate postoperative CB and more likely to experience spontaneous improvement or recurrence of coronal balance during follow-up. Severe extensor muscle degeneration and prominent asymmetric bilateral PSM degeneration represent potential risk factors for persistent CIB and recurrent CIB. It is crucial to assess the dynamic change during the follow-up period as long-term prognosis may be impacted if CB deteriorates, or otherwise develops during follow-up.Level of Evidence:3.

ObjectiveDue to the low incidence of achondroplasia (Ach), there is a relative lack of research on the treatment and management of spinal complications of Ach. Characteristics and interventions for spinal complications in patients with Ach are in urgent need of investigation. This study aimed to summarize the common spinal complications in patients with Ach and the corresponding treatment strategies.MethodsThis study is a retrospective case series. We retrospectively collected and analyzed Ach cases who presented to our hospital with neurological symptoms due to skeletal anomalies between February 2003 and October 2023. A total of seven patients were included, four males (57.1%) and three females (42.9%) with a mean age of 38.57 years. Patient pain/numbness visual analog scale (VAS), preoperative Oswestry disability index (ODI), development of neurological complaints, and presentation of skeletal abnormalities were collected and followed up routinely at 3, 6, 12 and 24 months postoperatively. The relevant literature was reviewed.ResultsSeven patients were included in this series. The mean preoperative VAS was 4, and the mean preoperative ODI was 50.98%. All patients had concomitant spinal stenosis, four with thoracolumbar kyphosis (TLK), and one with scoliosis. Six of the seven patients underwent surgery, and one patient received conservative treatment. In the routine follow‐ups, all patients experienced satisfactory relief of symptoms. Only one of the seven patients developed a new rare lesion adjacent to the primary segments. Six months after the first surgery, a follow‐up visit revealed thoracic spinal stenosis caused by ossification of the ligamentum flavum, and his symptoms were relieved after thoracic decompression surgery.ConclusionsAch seriously affects the skeletal development of patients and can lead to the development of spinal stenosis, spinal deformities, and other complications of the locomotor system. Surgery remains the primary treatment for complications of the musculoskeletal system. Specific surgical approaches and comprehensive, long‐term management are critical to the treatment of patients with spinal complications.

Numerous oil-water mixtures produced through industrial production processes and daily activities pollute the ecological environment and pose risks to human health. The development of materials with high oil-water mixture separation efficiency can promote the recycling of oil and water resources and effectively prevent environmental pollution caused by their direct discharge. Most of the current oil-water separation materials consist of foam, aerogel, and other porous materials. Among these materials, polyurethane exhibits good biodegradability, mechanical properties, large pore volume, low cost, wear resistance, and water resistance in oil-water mixture separation applications. However, pure polyurethane foam is characterized by low adsorption separation efficiency, insufficient recyclability, and high flammability. Therefore, modifying polyurethane to improve the oil-water mixture separation efficiency is vital. In this review, the methods and mechanisms of polyurethane modified materials used for oil-water mixture separation are reviewed, and their future research and application directions are prospected.

Study design.Prospective cohort study. Objective.Investigating the ability of a 6-minute walking test (6MWT) to assess functional status in patients with cervical spondylotic myelopathy (CSM). Summary of Background Data.The 6MWT provides an objective assessment of a patient's ability to walk. There is the potential for its application to the assessment of functional status in patients with CSM. Materials and Methods.One hundred thirty-five patients from our institution were prospectively enrolled from July 2022 to August 2023. A control group of age-matched and sex-matched healthy individuals was established. The 6MWT was conducted in strict accordance with established guidelines. The Nurick score, the Prolo score, the Cooper-myelopathy-scale score (CMS), the Japanese Orthopedic Association score (JOA) and the European-myelopathy-scale score (EMS) were assessed preoperatively. Visual Analog Scale (VAS) for pain or numbness and Oswestry Neck Disability Index (NDI) were also collected. Radiographic parameters were measured and recorded. Continuous variables between patients and controls were compared by applying the t test. The chi(2) test was used to compare gender ratios between groups. Pearson correlation analysis was used to analyze the association between continuous variables and ordinal variables. Subgroups of CSM patients were analyzed according to global spinal alignment types based on whether the SVA was >= 50 mm. Clinical scores and imaging parameters were compared by t test. Results.The preoperative 6-minute walking distance (6MWD) of CSM patients was 309.34 +/- 116.71 m, which was significantly lower than that of the controls (464.30 +/- 52.59 m, P<0.01). The 6MWD was significantly correlated with scores on all clinical scales except the VAS. CMS Lower extremity score had the strongest correlation with preoperative 6MWD in CSM patients (r=-0.794, P<0.01). Of the sagittal alignment parameters, only C7 sagittal vertical axis (SVA) and T1 slope were significantly correlated with 6MWD(r=-0.510, -0.360, respectively). CSM patients with SVA >50 mm had significantly lower 6MWD than CSM patients with SVA <= 50 mm (168.00 +/- 137.26 vs. 346.24 +/- 84.27 m, P<.01). Conclusions.The 6MWD of CSM patients was significantly lower than that of the healthy population and correlated well with commonly used clinical scales. The 6MWD can potentially assist in the assessment of functional status in patients with CSM.

The strategy of coupling transition metal and N-doped carbon catalysts have garnered great attention in catalytic ozonation. To overcome the inferior mass transfer of O3, we prepared a hetero-structure catalyst (Co3O4@Co-N-CMK3), which was composed of Co3O4 nanoparticles (NPs) and cobalt-nitrogen doped ordered mesoporous carbon. Co3O4@Co-N-CMK3 displayed a uniformly arranged long-range mesoporous channel structure with large surface area (537.24 m2/g). The adsorption efficiency of ATZ (10 mu M) was 55% at 15 min in presence of 0.05 g/L catalyst. After aeration of 3.5 mg/L O3 gas (50 mL min-1), the ATZ removal increased to 99.6% with rate constant of 0.354 min -1 in Co3O4@Co-N-CMK3/O3, 35.4-fold that in ozonation. The turnover frequency (TOF) value of Co3O4@Co-N-CMK3 reached 7.08 min-1 g-1, which was 2.2-93.2 folds higher than the reported ozonation catalysts. Co3O4@Co-N-CMK3 displayed the adsorption performance for ATZ and could activate O3 into center dot O2- and center dot OH effectively. The equivalent to Co2+ and equivalent to Co-Nx were main active sites. The synergy between Co3O4 and Co-N-CMK3 accelerated interface electron transfer, which was conducive to the redox of equivalent to Co2+/equivalent to Co3+. The degradation pathway and intermediates toxicity were speculated using HPLC-MS measurement and Toxicity Estimation Software Tool simulation. The stability of Co3O4@Co-N-CMK3 for ATZ removal was certified by five consecutive experiments in catalytic ozonation. Moreover, the Co3O4@Co-N-CMK3/O3 process had good applicability to common anions and humic acid, real water and different pollutants.

Nitrate pollution in surface water poses a significant threat to drinking water safety. The integration of electrocatalytic reduction reaction of nitrate (NO3RR) to ammonia with ammonia collection processes offers a sustainable approach to nitrogen recovery from nitrate-polluted surface water. However, the low catalytic activity of existing catalysts has resulted in excessive energy consumption for NO3RR. Herein, we developed a facile approach of electrochemical reduction to generate oxygen vacancy (Ov) on zinc oxide nanoparticles (ZnO1-x NPs) to enhance catalytic activity. The ZnO1-x NPs achieved a high NH3-N selectivity of 92.4% and NH3-N production rate of 1007.9 [Formula: see text] h-1 m-2 at -0.65 V vs. RHE in 22.5 mg L-1NO3--N, surpassing both pristine ZnO and the majority of catalysts reported in the literature. DFT calculations with in-situ Raman spectroscopy and ESR analysis revealed that the presence of Ov significantly increased the affinity for the NO3- (nitrate) and key intermediate of NO2- (nitrite). The strong adsorption of NO3- on Ov decreased the energy barrier of potential determining step (NO3- →∗NO3) from 0.49 to 0.1 eV, boosting the reaction rate. Furthermore, the strong adsorption of NO2- on Ov prevented its escape from the active sites, thereby minimizing NO2- by-product formation and enhancing ammonia selectivity. Moreover, the NO3RR, when coupled with a membrane separation process, achieved a 100% nitrogen recycling efficiency with low energy consumption of 0.55 kWh molN-1 at a flow rate below 112 mL min-1 for the treatment of nitrate-polluted lake water. These results demonstrate that ZnO1-x NPs are a reliable catalytic material for NO₃RR, enabling the development of a sustainable technology for nitrogen recovery from nitrate-polluted surface water.

To date, several molecules have been found to facilitate iron influx, while the types of iron influx channels remain to be elucidated. Here, Piezo1 channel was identified as a key iron transporter in response to mechanical stress. Piezo1-mediated iron overload disturbed iron metabolism and exaggerated ferroptosis in nucleus pulposus cells (NPCs). Importantly, Piezo1-induced iron influx was independent of the transferrin receptor (TFRC), a well-recognized iron gatekeeper. Furthermore, pharmacological inactivation of Piezo1 profoundly reduced iron accumulation, alleviated mitochondrial ROS, and suppressed ferroptotic alterations in stimulation of mechanical stress. Moreover, conditional knockout of Piezo1 (Col2a1-CreERT Piezo1flox/flox) attenuated the mechanical injury-induced intervertebral disc degeneration (IVDD). Notably, the protective effect of Piezo1 deficiency in IVDD was dampened in Piezo1/Gpx4 conditional double knockout (cDKO) mice (Col2a1-CreERT Piezo1flox/flox/Gpx4flox/flox). These findings suggest that Piezo1 is a potential determinant of iron influx, indicating that the Piezo1-iron-ferroptosis axis might shed light on the treatment of mechanical stress-induced diseases.