Enhanced Fenton-Like Catalysis via Interfacial Regulation of g-C3N4 for Efficient Aromatic Organic Pollutant Degradation.

For the efficient degradation of organic pollutants with the goal of reducing the water environment pollution, we employed an alkaline hydrothermal treatment on primeval g-C3N4 to synthesize a hydroxyl-grafted g-C3N4 (CN-0.5) material, from which we engineered a novel Fenton-like catalyst, known as Cu-CN-0.5. The introduction of numerous hydroxyl functional groups allowed the CN-0.5 substrate to stably fix active copper oxide particles through surface complexation, resulting in a low Cu leaching rate during a Cu-CN-0.5 Fenton-like process. A sequence of characterization techniques and theoretical calculations uncovered that interfacial complexation induced charge redistribution on the Cu-CN-0.5 surface. Specifically, some of the π electrons in the tris-s-triazine units were transferred to the copper oxide particles along the newly formed chemical bonds (C(π)-O-Cu), forming a π-deficient area on the tris-s-triazine plane near the complexation site. In a typical Cu-CN-0.5 Fenton-like process, a stable π-π interaction was established due to the favorable positive-negative match of electrostatic potential between the aromatic pollutants and π-deficient areas, leading to a significant improvement in Cu-CN-0.5's adsorption capacity for aromatic pollutants. Furthermore, pollutants also delivered electrons to the Cu-CN-0.5 Fenton-like system via a "through-space" approach, which suppressed the futile oxidation of H2O2 in reducing the high-valent Cu2+ and significantly improved the generation efficiency of •OH with high oxidative capacity. As expected, Cu-CN-0.5 not only exhibited an efficient Fenton degradation for several typical aromatic organic pollutants, but also demonstrated both a low metal leaching rate (0.12 mg/L) and a H2O2 utilization rate exceeding 80%. The distinctive Fenton degradation mechanism substantiated the potential of the as-prepared material for effective wastewater treatment applications.

Biomass-derived cellulose nanocrystals modified nZVI for enhanced tetrabromobisphenol A (TBBPA) removal.

Nano zero-valent iron (nZVI) is an advanced environmental functional material for the degradation of tetrabromobisphenol A (TBBPA). However, high surface energy, self-agglomeration and low electron selectivity limit degradation rate and complete debromination of bare nZVI. Herein, we presented biomass-derived cellulose nanocrystals (CNC) modified nZVI (CNC/nZVI) for enhanced TBBPA removal. The effects of raw material (straw, filter paper and cotton), process (time, type and concentration of acid hydrolysis) and synthesis methods (in-situ and ex-situ) on fabrication of CNC/nZVI were systematically evaluated based on TBBPA removal performance. The optimized CNC-S/nZVI(in) was prepared via in-situ liquid-phase reduction using straw as raw material of CNC and processing through 44 % H2SO4 for 165 min. Characterizations illustrated nZVI was anchored to the active sites at CNC interface through electrostatic interactions, hydrogen bonds and FeO coordinations. The batch experiments showed 0.5 g/L CNC-S/nZVI(in) achieved 96.5 % removal efficiency at pH = 7 for 10 mg/L initial TBBPA. The enhanced TBBPA dehalogenation by CNC-S/nZVI(in), involving in initial adsorption, reduction process and partial detachment of debrominated products, were possibly attributed to elevated pre-adsorption capacity and high-efficiency delivery of electrons synergistically. This study indicated that fine-tuned fabrication of CNC/nZVI could potentially be a promising alternative for remediation of TBBPA-contaminated aquatic environments.

Surface wettability control and electron transport regulation in zerovalent iron for enhanced removal of emerging polystyrene microplastics-heavy metal contaminants.

Emerging microplastics-heavy metal (MPs-HM) contaminants in wastewaters pose an emerging health and environmental risk due to their persistence and increasing ecological risks (e.g., "Trojan horse" effect). Hence, removing MPs in solution and preventing secondary releases of HM has become a key challenge when tackling with MPs pollution. Leveraging the hydrophobic nature of MPs and the electron transfer efficiency from Fe0 to HM, we demonstrate an alkylated and sulfidated nanoscale zerovalent iron (AS-nZVI) featuring a delicate "core-shell-hydrophobic film" nanostructure. Exemplified by polystyrene (PS) MPs-Pb(II) removal, the three nanocomponents offer synergistic functions for the rapid separation of MPs, as well as the reduction and stabilization of Pb(II). The outmost hydrophobic film of AS-nZVI greatly improves the anticorrosion performance of nanoscale zerovalent iron and the enrichment abilities of hydrophobic MPs, achieving a maximum removal capacity of MPs to 2725.87 mgMPs·gFe-1. This MPs enrichment promotes the subsequent reductive removal of Pb(II) through the electron transfer from the iron core of AS-nZVI to Pb(II), a process further strengthened by the introduced sulfur. When considering the inevitable aging of MPs in wastewaters due to mechanical wear or microbial degradation, our study concurrently examines the efficiencies and behaviors of AS-nZVI in removing virgin-MPs-Pb(II) and aged-MPs-Pb(II). The batch results reveal that AS-nZVI has an exceptional ability to remove above 99.6 % Pb(II) for all reaction systems. Overall, this work marks a pioneering effort in highlighting the importance of MPs-toxin combinations in dealing with MPs contamination and in demonstrating the utility of nZVI techniques for MPs-contaminated water purification.

Harmonizing the cyano-group and Na to enhance selective photocatalytic O2 activation on carbon nitride for refractory pollutant degradation.

Manipulating exciton dissociation and charge-carrier transfer processes to selectively generate free radicals of more robust photocatalytic oxidation capacity for mineralizing refractory pollutants remains challenging. Herein, we propose a strategy by simultaneously introducing the cyano-group and Na into graphitic carbon nitride (CN) to obtain CN-Cy-Na, which makes the charge-carrier transfer pathways the dominant process and consequently achieves the selective generation of free radicals. Briefly, the cyano-group intensifies the local charge density of CN, offering a potential well to attract the hole of exciton, which accelerates the exciton dissociation. Meanwhile, the separated electron transfers efficiently under the robust built-in electric field induced by the cyano-group and Na, and eventually accumulates in the heptazine ring of CN for the following O2 reduction due to the reinforced electron sink effect caused by Na. As a result, CN-Cy-Na exhibits 4.42 mmol L-1 h-1 productivity with 97.6% selectivity for free radicals and achieves 82.1% total organic carbon removal efficiency in the tetracycline photodegradation within 6 h. Additionally, CN-Cy-Na also shows outstanding photodegradation efficiency of refractory pollutants, including antibiotics, pesticide plastic additives, and dyes. This work presents an innovative approach to manipulating the exciton effect and enhancing charge-carrier mobility within two-dimensional photocatalysts, opening an avenue for precise control of free radical generation.

Associations of recurrent lumbar disc herniation after percutaneous endoscopic lumbar discectomy with age, body mass index, modic change, disc degeneration and sacral slope: A quantitative review.

Recurrent lumbar disc herniation (rLDH) seriously affects the quality of life of patients and increases the medical burden. The purpose of the present study was to determine the risk factors for rLDH after percutaneous endoscopic lumbar discectomy (PELD). The PubMed, Cochrane Library and Embase databases were searched for studies on the factors associated with rLDH after PELD. The databases were searched from inception to March 30, 2023. The combined effects of categorical variables and continuous variables were measured using odds ratios (ORs) and weighted mean differences (WMDs), respectively, and their corresponding 95% confidence intervals (CIs) were calculated. RevMan 5.3 software was used for data analysis. A total of 9 case-control studies were included in this meta-analysis, comprising 5,446 patients. This study explored a total of 18 potential risk factors for rLDH after PELD; ultimately, 5 factors were associated with the risk of rLDH. Meta-analysis showed that older age (WMD=6.49, 95% CI: 2.52 to 10.46), greater body mass index (WMD=1.16, 95% CI: 0.69 to 1.62), modic change (OR=2.48, 95% CI: 1.54 to 3.99), Pfirrmann grade ≥4 (OR=2.84, 95% CI: 1.3 to 6.16) and greater sacral slope angle (WMD=3.48, 95% CI: 0.53 to 6.42) were risk factors for rLDH after PELD. The risk factors identified in the present study may enable clinicians to identify high-risk populations early and to select appropriate surgical procedures to reduce the risk of rLDH. Perioperative interventions targeting the modifiable factors identified in this study may be beneficial for reducing the risk of rLDH.

Accumulation, translocation, and fractionation of rare earth elements (REEs) in fern species of hyperaccumulators and non-hyperaccumulators growing in urban areas.

The issue of ion-adsorption type rare earth deposits (IADs) in urban areas of South China has garnered significant attention due to its environmental implications. Hyperaccumulator-based phytoremediation is a potentially effective solution for reducing the environmental impact of IADs in urban areas, particularly using ferns as they are known to be REE hyperaccumulators. However, the ability of different fern species to accumulate REEs in urban areas remains unknown. In this study, four fern species, including known hyperaccumulators (Dicranopteris linearis and Blechnum orientale) and other ferns (Pteris ensiformis and Cibotium barometz), were studied to investigate their REE accumulation abilities in the Guangzhou urban area. The aboveground parts of Dicranopteris linearis (848.7 µg g-1) and Blechum orientale (1046.8 µg g-1) have been found to accumulate high concentrations of REEs, demonstrating they probably can be applied for phytoremediation in the natural environments. Despite having lower REE concentrations than REE hyperaccumulators, Pteris ensiformis and Cibotium barometz still probably have the function as phytostabilizers in urban areas, as REEs can be enriched in their roots beyond the normal levels of plants. The enrichment of REEs in ferns is influenced by the availability of various nutrients (K, Ca, Fe, and P), which probably can be associated with different growth processes. The four fern species show LREE enrichment, moderate Eu anomalies and different Ce anomalies. It is difficult to absorb and transfer Ce to the aboveground parts of Blechnum orientale and Cibotium barometz. The study also identified selective enrichment of Ce in Pteris ensiformis, which has potential for comprehensive extraction of REEs when combined with other REE hyperaccumulators. REE fractionations are probably determined by the specific characteristics of different fern parts. Overall, these findings provide insights for addressing potential environmental problems related to IADs and offer guidelines for phytoremediation technology in addressing high REE levels in urban areas.

Machine-Learning-Assisted Optimization of a Single-Atom Coordination Environment for Accelerated Fenton Catalysis.

Machine learning (ML) algorithms will be enablers in revolutionizing traditional methods of materials optimization. Here, we broaden the use of ML to assist the construction of Fenton-like single-atom catalysts (SACs) by developing a methodology including model building, training, and prediction. Our approach can efficiently extract synthesis parameters that exert a substantial influence on Fenton activity and accurately predict the phenol degradation rate k of SACs with a mean error of ±0.018 min-1. The extended synthesis window with accelerated learning enables the realization that the heating temperatures during SAC synthesis significantly influence the Fe-N coordination number, which ultimately dictates their performance. Through ML-guided optimization, a highly efficient SAC dominated by Fe-N5 sites with exceptional Fenton activity (k = 0.158 min-1) is identified. Our work provides an example for ML-assisted optimization of single-atom coordination environments and illuminates the feasibility of ML in accelerating the development of high-performance catalysts.

Self-Powered Electrodeposition System for Sub-10-nm Silver Nanoparticles with High-Efficiency Antibacterial Activity.

Recently, silver nanoparticles (AgNPs) have been widely applied in sterilization due to their excellent antibacterial properties. However, AgNPs require rigorous storage conditions because their antibacterial performances are significantly affected by environmental conditions. Instant fabrication provides a remedy for this drawback. In this study, we propose a self-powered electrodeposition system to synthesize sub-10-nm AgNPs, consisting of a triboelectric nanogenerator (TENG) as the self-powered source, a capacitor for storing electrical energy from the TENG, and an electrochemical component for electrodeposition. The self-powered system with larger capacitance and discharging voltage tends to deliver smaller AgNPs due to the nucleation mechanism dominated by current density. Furthermore, antibacterial tests reveal that compared to direct current (DC) electrodeposition, the TENG-based electrodeposition can synthesize finer-sized AgNPs (<10 nm) with overwhelming antibacterial effect against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) (with 100% efficiency at 2 h). This work provides a new strategy for the self-powered, instant, and controllable electrodeposition of nanoparticles.

Phosphate modified magnetite@ferrihydrite as an magnetic adsorbent for Cd(II) removal from water, soil, and sediment.

This work successfully fabricated a novel magnetic adsorbent, i.e., phosphate modified magnetite@ferrihydrite (Mag@Fh-P), and explored its potential application for Cd(II) removal from water, soil, and sediment. To synthesize the adsorbent, ferrihydrite-coated magnetite (Mag@Fh) was firstly developed with partially acid-dissolved natural magnetite particles, followed by in-situ synthesis of ferrihydrite on magnetite surface via alkali addition. Selection of natural magnetite as iron source for ferrihydrite synthesis and as magnetic core is believed to save the cost of adsorbent. Then, phosphate was loaded on Mag@Fh by impregnation-heating treatment to produce Mag@Fh-P. Batch adsorption experiments revealed that the Cd(II) adsorption on Mag@Fh-P could reach equilibrium within 60 min, and the calculated adsorption capacity using Langmuir model was 64.1 mg/g, which was significantly higher than that on magnetite (0.44 mg/g) and Mag@Fh (23.9 mg/g). The results from X-ray photoelectron spectroscopy analysis and batch adsorption experiments confirmed that both ligand exchange and electrostatic attraction contributed to Cd(II) adsorption. Besides, Mag@Fh-P can also be an efficient amendment for soil and sediment remediation. The spent Mag@Fh-P could be easily recovered via magnetic separation, accompanied by the significant decrease in total Cd(II) concentration in soil/sediment. At an adsorbent dosage of 2 wt%, 0.82 and 0.74 mg/kg of total Cd(II) in soil and sediment was removed, respectively. In all, the synthesized Mag@Fh-P as adsorbent has the merits of cost effectiveness, fast adsorption rate, high adsorption capacity, and easy separation, and thus it has promising application for the removal of heavy metal cations from water, soil, and sediment.

Object-Based Shadow Index via Illumination Intensity from High Resolution Satellite Images over Urban Areas.

For multi-spectral remote sensing imagery, accurate shadow extraction is of great significance for overcoming the information loss caused by high buildings and the solar incidence angle in urban remote sensing. However, diverse solar illumination conditions, similarities between shadows, and other dark land features bring uncertainties and deviations to shadow extraction processes and results. In this paper, we classify shadows as either strong or weak based on the ratio between ambient light intensity and direct light intensity, and use the fractal net evolution approach (FNEA), which is a multi-scale segmentation method based on spectral and shape heterogeneity, to reduce the interference of salt and pepper noise and relieve the error of misdiagnosing land covers with high reflectivity in shaded regions as unshaded ones. Subsequently, an object-based shadow index (OSI) is presented according to the illumination intensities of different reflectance features, as well as using the normalized difference water index (NDWI) and near infrared (NIR) band to highlight shadows and eliminate water body interference. The data from three high-spatial-resolution satellites-WorldView-2 (WV-2), WorldView-3 (WV-3), and GaoFen-2 (GF-2)-were used to test the methods and verify the robustness of the OSI. The results show that the OSI index performed well regarding both strong and weak shadows with the user accuracy and the producer accuracy both above 90%, while the four other existing indexes that were tested were not effective at diverse solar illumination conditions. In addition, all the disturbances from water body were excluded well when using the OSI, except for the GF-2 data in weak shadows.

Facile synthesis of Al/Fe bimetallic (oxyhydr)oxide-coated magnetite for efficient removal of fluoride from water.

In this work, we developed a novel magnetic bimetallic Al/Fe (oxyhydr)oxide adsorbent through a facile and cost-effective method and explored its potential to adsorb fluoride in water. Its synthesis involved corrosion of natural magnetite in aluminium chloride solution, followed by titration with NaOH solution for in-situ synthesis of Al/Fe (oxyhydr)oxide-coated magnetite (Mag@Al2Fe). Characterization data indicated a uniform coating of Al/Fe (oxyhydr)oxide on magnetite, and the resulting composite possessed large specific surface area (∼90 m2/g) and good magnetic property. In batch adsorption experiments, the isotherm and kinetic data fitted well to the Langmuir model and pseudo-second-order model, respectively. The maximum adsorption capacity of Mag@Al2Fe is 26.5 mg/g, which was much higher than natural magnetite (0.44 mg/g). Moreover, this material retained high adsorption capacity toward fluoride within a wide pH range (3.0-8.0) and offered facile magnetic separation from water. Influence of competing ions was also evaluated which showed that the presence of Cl- and NO3 - posed negligible interference, while HCO3 - and SO4 2- had negative effects on fluoride adsorption. Thermodynamic investigations revealed that fluoride adsorption was exothermic and spontaneous. The observed increase in solution pH and formation of Al-F and Fe-F bonds (as indicated by XPS analysis) after fluoride adsorption suggested the major adsorption mechanism of ligand exchange. Besides, the adsorption/desorption cycle studies demonstrated the well-retained performance of Mag@Al2Fe for repeated application after regeneration by 0.5 mol/L NaOH solution. Facile synthesis, high defluoridation, lower cost, and quick separation of Mag@Al2Fe indicates its promising potential for drinking water defluoridation.

Phosphate addition diminishes the efficacy of wollastonite in decreasing Cd uptake by rice (Oryza sativa L.) in paddy soil.

Cadmium (Cd) contamination in paddy soils poses food security risks and public health concerns. Exploring effective strategies to reduce rice grain Cd is an urgent need. In this study, field plot experiments were conducted to evaluate the effects of wollastonite application with or without phosphate (P) addition on Cd accumulation in rice (Oryza sativa L.). Co-application of P and wollastonite showed greater efficiency than wollastonite amendments alone in raising soil pH and CEC and decreasing soil Cd availability. Cd concentration in brown rice was decreased by 71% under the wollastonite treatment alone, but was decreased by only 29-39% when wollastonite was coupled with different P amendments. This seeming contradiction could be ascribed to the dramatic decline in the phytoavailability of manganese (Mn) and the increase in molar ratio of iron (Fe) to Mn (Fe/Mn) in Fe plaques on root surfaces in the presence of P additions. Significant negative correlations between Mn and Cd in rice plants and positive correlations between Fe/Mn in Fe plaque and Cd in rice plants indicated that P-induced soil Mn deficiency and reduced Mn in Fe plaque impeded the alleviation of Cd accumulation in rice. Application of wollastonite in Si-deficient paddy soils was effective in reducing rice Cd accumulation while boosting rice yield, but co-application of P and wollastonite was counterproductive and should be avoided. This work emphasized that a better understanding of the relationships between Cd and related mineral nutrient uptake would be helpful in developing more efficient measures to reduce rice grain Cd.

Correction: In situ synthesis of a silicon flake/nitrogen-doped graphene-like carbon composite from organoclay for high-performance lithium-ion battery anodes.

Correction for 'In situ synthesis of a silicon flake/nitrogen-doped graphene-like carbon composite from organoclay for high-performance lithium-ion battery anodes' by Qingze Chen et al., Chem. Commun., 2019, 55, 2644-2647.

In situ synthesis of a silicon flake/nitrogen-doped graphene-like carbon composite from organoclay for high-performance lithium-ion battery anodes.

A silicon flake/nitrogen-doped graphene-like carbon composite was prepared from organoclay via an in situ strategy, involving carbonization followed by low-temperature aluminothermic reduction. The pre-formed carbon sheets within the confined interlayer space of clay acted as nanotemplates for in situ synthesizing silicon flakes. As a lithium-ion battery anode, the composite exhibited excellent electrochemical properties.

Superior adsorption of phosphate by ferrihydrite-coated and lanthanum-decorated magnetite.

Present study reports the successful development of a novel lanthanum (La)-based magnetic adsorbent and its use for phosphate removal from water. For its synthesis, natural magnetite (Mag), Fe3O4, was subjected to partial dissolution in HCl solution and the obtained suspension was mixed with an alkaline solution for in-situ synthesis of ferrihydrite (Fh)-coated Mag (Mag@Fh). Mag@Fh was then decorated with La (hydr)oxides followed by calcination to produce Fh-coated and La-decorated Mag (Mag@Fh-La). Obtained Mag@Fh-La represented high phosphate adsorption capacity (44.8 mg P/g at 15.7% La in its structure) and La usage efficiency. Moreover, Mag@Fh-La retained its high adsorption capacity (>35.0 mg P/g) over a wide range of equilibrium solution pH (3.2-10.7). The combination of FTIR, XPS analysis and adsorption experiments revealed that ligand exchange and electrostatic attraction were the main mechanisms that jointly facilitated the adsorption of phosphate. Adsorption-desorption cycle studies confirmed the well-retained adsorption efficiency of regenerated Mag@Fh-La for repeated applications. Final experiments with real domestic wastewater (initial phosphate concentration of 1.7 mg/L) revealed that 0.2 g/L Mag@Fh-La efficiently reduced the phosphate concentration to below 0.02 mg/L. Overall, this work clearly highlights that the synthesized novel adsorbent has promising applications in phosphate removal from real wastewater.

Converting Spent Cu/Fe Layered Double Hydroxide into Cr(VI) Reductant and Porous Carbon Material.

Recycling solid waste as functional materials is important for both environmental remediation and resource recycling. This study attempts to recycle spent Cu/Fe layered double hydroxide (Cu/Fe-LDH) which is generated from the adsorption of dyes by converting to Cr(VI) reductant and porous carbon material. Results showed that the obtained reductant was mainly composed of Fe0 and Cu0, and exhibited good reductive activity toward Cr(VI). The species of Fe0, Fe2+, Cu0, and Cu+ all favored the reduction of Cr(VI) according to X-ray photoelectron spectroscopy analysis. During Cr(VI) removal, solution pH could increase to neutral which caused the metal ions to precipitate near completion. On the other hand, the spent Cu/Fe-LDH could be employed to produce porous carbon materials, and the generated waste metals solution herein could be reused for LDH synthesis. Specific surface areas of the obtained carbon materials varied from 141.3-744.2 m2/g with changes in adsorbed amount of dyes on the LDH. This study illustrates that all the components of wastes can be useful resources, offering a simple recycling approach for similar organic-inorganic solid wastes. This work also enlightens us that designing a proper initial product is crucial to make waste recycling simpler.