Polyanionic transition metal polyphosphate (TMPO)‐type Na3V2(PO4)2O2F (NVPO2F) is promising as cathode for large‐scale sodium‐ion batteries (SIBs) on account of its considerable capacity and highly ...stable structure. However, the redox of transition metal and phase transitions along with the (de)intercalation of Na+ lead to its slow kinetics and inferior rate performance. Herein, chlorine (Cl) is applied as a heteropical dopant to obtain Cl‐doped NVPO2F (NVPO2−xClxF) cathode material for SIBs. Density functional theory investigation reveals that Cl doping tunes the localized electronic density and structure in NVPO2F lattice, causing the electron redistribution on vanadium center and dangling anions. Hence, the NVPO2−xClxF cathode exhibits a revised redox behavior of vanadium for Na+ extraction/insertion, increases Na+ diffusion rate, as well as lowers charge transfer resistance. A Na+ storage mechanism of reversible transformations between three phases and V4+/V5+ redox couple for NVPO2−xClxF cathode is verified. The NVPO2−xClxF cathode reveals a high rate capacity of ≈63 mAh g−1 at 30C and great cycle stability over 1000 cycles at 10C. More importantly, outstanding rate property (314 Wh kg−1 at 5850 W kg−1) and cycling capability are obtained for the NVPO2−xClxF//3DC@Se full cell. This study demonstrates a brand‐new strategy to prepare advanced cathode materials for superior SIBs.
Cl‐doped Na3V2(PO4)2O2F (NVPO2−xClxF) cathode material is prepared for the first time via a facile chemical vapor replacing process. The density functional theory investigations verify that the Cl doping tunes the electronic structure and causes the electron redistribution on vanadium center/dangling anions. Therefore, a revised redox behavior of vanadium and increased Na+ diffusivity are achieved, enabling superior rate property.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
As promising cathode for sodium‐ion batteries, Na+ Superionic Conductor (NASICON)‐type materials have attracted attention owing to their excellent structural stability, superior ionic conductivity, ...and small volume expansion. However, the vanadium‐based NASICON‐type cathode with the biotoxicity and exorbitant price of V element and the iron‐based cathode with low mean working voltage as well as the intrinsic poor electronic conductivity of polyanionic compounds hinder their practical applications. Herein, a double‐carbon‐layer decorated heterogeneous composite, Na3V2(PO4)3‐Na3Fe2(PO4)(P2O7) (NVFPP/C/G), is successfully prepared for addressing these limitations. Due to their synergistic effect, NVFPP/C/G exhibits excellent electrochemical performance in half‐cell system and superior full‐cell performance when matched with hard carbon anode. Furthermore, the phase composition, electrode kinetics, and phase transition are confirmed by combined analyses of slow scanning power X‐ray diffraction, high‐resolution transmission electron microscopy, cyclic voltammetry with various scan rates, galvanostatic intermittent titration technique, ex situ X‐ray photoelectron spectra, and in situ X‐ray diffraction. This study portends a promising strategy to utilize composite structure engineering for developing advanced polyanionic cathodes.
A double‐carbon‐layer decorated heterogeneous Na3V2(PO4)3‐Na3Fe2(PO4)(P2O7) composite is proposed as cathode for sodium‐ion batteries. Due to the synergistic effect, it exhibits excellent electrochemical performance in half‐cell system and superior full‐cell performance. The heterogeneous composite structure engineering strategy provides a new approach to design high‐performance polyanionic cathodes for batteries.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Iron metabolism in inflammation has been mostly characterized in macrophages exposed to pathogens or inflammatory conditions. The aim of this study is to investigate the cross-regulatory interactions ...between M1 macrophage polarization and iron metabolism. Firstly, we characterized the transcription of genes related to iron homeostasis in M1 RAW264.7 macrophages stimulated by IFN-γ. The molecular signature of M1 macrophages showed high levels of iron storage (ferritin), a low level of iron export (ferroportin), and changes of iron regulators (hepcidin and transferrin receptors), which favour iron sequestration in the reticuloendothelial system and are benefit for inflammatory disorders. Then, we evaluated the effect of iron on M1 macrophage polarization. Iron significantly reduced mRNA levels of IL-6, IL-1β, TNF-α, and iNOS produced by IFN-γ-polarized M1 macrophages. Immunofluorescence analysis showed that iron also reduced iNOS production. However, iron did not compromise but enhanced the ability of M1-polarized macrophages to phagocytose FITC-dextran. Moreover, we demonstrated that STAT1 inhibition was required for reduction of iNOS and M1-related cytokines production by the present of iron. Together, these findings indicated that iron decreased polarization of M1 macrophages and inhibited the production of the proinflammatory cytokines. The results expanded our knowledge about the role of iron in macrophage polarization.
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DOBA, FZAB, GIS, IJS, IZUM, KILJ, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBMB, SIK, UILJ, UKNU, UL, UM, UPUK
Summary
Bacterial secondary metabolites are rich sources of novel drug leads. The diversity of secondary metabolite biosynthetic gene clusters (BGCs) in genome‐sequenced bacteria, which will provide ...crucial information for the efficient discovery of novel natural products, has not been systematically investigated. Here, the distribution and genetic diversity of BGCs in 10 121 prokaryotic genomes (across 68 phyla) were obtained from their PRISM4 outputs using a custom python script. A total of 18 043 BGCs are detected from 5743 genomes with non‐ribosomal peptide synthetases (25.4%) and polyketides (15.9%) as the dominant classes of BGCs. Bacterial strains harbouring the largest number of BGCs are revealed and BGC count in strains of some genera vary greatly, suggesting the necessity of individually evaluating the secondary metabolism potential. Additional analysis against 102 strains of discovered bacterial genera with abundant amounts of BGCs confirms that Kutzneria, Kibdelosporangium, Moorea, Saccharothrix, Cystobacter, Archangium, Actinosynnema, Kitasatospora, and Nocardia, may also be important sources of natural products and worthy of priority investigation. Comparative analysis of BGCs within these genera indicates the great diversity and novelty of the BGCs. This study presents an atlas of bacterial secondary metabolite BGCs that provides a lot of key information for the targeted discovery of novel natural products.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The structural phase transition (SPT) and metal-insulator phase transition (MIT) always occur simultaneously upon heating from the low-temperature insulator M
1
phase to the high-temperature metal R ...phase in vanadium dioxide, and it is still unclear which one of Mott correlation and Peierls distortion plays a decisive role in the thermally induced phase transition (PT) since 1959. Our density functional theory (DFT)-based calculations revealed that the intermediate phase in the PT, the so-called monoclinic metal phase, is a zero indirect band gap semimetal (
P
2
1
/
c
space group) with a pseudo gap (199 meV). From the M
1
phase to the monoclinic metal phase, the band gap decreases gradually to zero, and the bonding lengths between vanadium-vanadium atoms remain nearly constant. The SPT and MIT from the intermediate structure to the R phase occur simultaneously with a sudden change of bonding lengths between vanadium-vanadium atoms, in which electrons can jump down rather than jump up to the conduction band minimum (CBM) from the valence band maximum (VBM) under thermal fluctuation in order to lower the total energy of the system to push forward the occurrence of PT. The electron jumping does not require additional energy from Coulomb repulsion between electrons even though it is always present. This SPT is a typical Peierls PT or a pseudo Mott PT rather than an actual Mott PT in the each of the two stages. Our conclusions provide a new understanding of SPT and MIT in vanadium dioxide that has been debated for more than 80 years.
The Peierls geometrical distortion rather than Mott electronic correlation always plays a decisive role in the thermally induced phase transition in which the presence of Coulomb repulsion between electrons does not have an effect.
The amount of spent lithium-ion batteries (LIBs) is constantly increasing as their popularity grows. It is important to develop a recycling method that cannot only convert large amounts of waste ...anode graphite into high value-added products but is also simple and environmentally friendly. In this work, spent graphite from an anode was transformed into a cathode for dual-ion batteries (DIBs) through a two-step treatment. This method enables the crystal structure and morphology of spent graphite to recover from the adverse effects of long cycling and be restored to a regular layered structure with appropriate layer spacing for anion intercalation. In addition, pyrolysis of the solid electrolyte interphase into an amorphous carbon layer prevents the electrode from degrading and improves its cycling performance. The recycled negative graphite has a high reversible capacity of 87 mAh g−1 at 200 mA g−1, and its rate performance when used as a cathode in DIBs is comparable to that of commercial graphite. This simple recycling idea turns spent anode graphite into a cathode material with attractive potential and superior electrochemical performance, genuinely achieving sustainable energy use. It also provides a new method for recovering exhausted batteries.
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•This study demonstrates a new reuse strategy for graphite anode in spent lithium-ion batteries.•The recovered graphite anode is reused as advanced cathode for Li-based dual-ion batteries.•It delivers excellent anion-storage properties including a specific capacity of 84 mAh g−1 and good rate performance.•This work broadens the high-value utilization ideas of recycled electrode materials from spent lithium-ion batteries..
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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•A novel magnetic nanocomposite was fabricated.•The magnetic nanocomposite could be used for high-efficient removing phenanthrene.•Theory calculations proposed the underlying ...intramolecular binding interactions.•Adsorption pathway and mechanism were studied.
Due to the toxicity and harmful of phenanthrene (PHE) pollutant to human health and the ecosystem, it is extremely urgent to find an accessible technique to efficiently alleviate PHE contamination risk. The Fe3O4-1.5benzhydrylamine (Fe3O4-1.5BENZHY) was successfully fabricated via the silane coupling and Schiff base substitution reaction. The Fe3O4 matrix facilitated the practical recycling efficiency and the aromatic nucleus of the benzhydrylamine could form π-π interaction with PHE molecular to improve adsorption performance. The benzhydrylamine loading amount and synthesis strategy could influence the adsorption capacity of the fabricated magnetic nanocomposite to some extent. Multiple characterization techniques were utilizedto assess the physical and chemical properties of the magnetic nanocomposite. The density functional theory (DFT) calculations combined with post-characterization not only revealed the π–π interaction of Fe3O4-1.5BENZHY and PHE was valid and usually existed in offset parallel stacking form, but also provided a deeper understanding of the underlying mechanism. Moreover, the stability and adsorption energy for all different configuration modes were evaluated by the LUMO-HOMO energy gap (EGAP) and electric distribution. The Fe3O4-1.5BENZHY exhibited a homogeneous surface and PHE molecules were adsorbed in a monolayer form, its adsorption capacity (26.07 mg g−1) was significantly higher compared with original Fe3O4 (13.28 mg g−1). This work helps broaden insight on the molecular binding mechanism of the adsorbent/adsorbate system and expands the modification strategies for magnetic oxide to achieve high-efficiency adsorption of hazardous polycyclic aromatic hydrocarbons.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The polyanion-type cathode materials for sodium-ion batteries are one of research hotspots in energy-storage areas. This review provides a reliable, concise and comprehensive summary of ...characterization techniques for polyanion-type cathode materials, aiming to understand the in-depth reaction mechanisms behind performance and provide an important guiding principle for designing high-performance polyanion-type cathode materials of SIBs.
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Polyanion-type cathode materials have grown in leaps and bounds and become one of the promising candidates for metal-ion batteries since the successful case of LiFePO4 in lithium-ion batteries, which own stable crystal structure, high thermal stability, good ionic conductivity, adjustable voltage and chemical composition. However, further exploration is requisite, such as, the change of crystal/electronic structure, reaction mechanism, and structure evolution during charge/discharge processes, which results from variety of crystal types and redox centers, anion and cationic doping/substitution, as well as transition metal ion migration in polyanion-type materials. In this review, we focus on the advanced characterization techniques referred in polyanion-type cathode materials of sodium-ion batteries, mainly consist of the structure-related, morphology-related, composition-related techniques and in-situ/operando techniques during charge/discharge processes. The respective detection mechanisms, scope of application, information available and limitations of each technique are discussed in detail, and the latest developments of these characterization techniques used in polyanion-type materials are summarized. Advanced characterization techniques play a crucial role in understanding the reaction mechanisms of electrode materials, and can provide an important guiding principle for designing high-performance polyanion-type cathode materials and further optimizing the battery systems of sodium-ion batteries.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
This work proposed a controllable synthesis of Ni-Mo catalyst supported inside multi-wall carbon nanotubes (CNTs). The results indicate that Ni improved the β-Mo2C formation and markedly promoted the ...benzofuran (BF) hydrogenation and hydrodeoxygenation activity of the catalysts. The synergistic interaction between Ni and Mo reached the maximum at a Ni/Mo molar ratio of 0.3, which could be favored by the proximity between the Ni and β-Mo2C particles inside the CNTs reaching a 99.5% of BF conversion to hydrogenated and deoxygenated products as 2,3-dihydrobenzofuran, octahydrobenzofuran, and ethylcyclohexane; in contrast, BF conversion on unsupported Ni-Mo2C-0.3 was only 0.7%. Deoxygenated products are favored under different conditions, such as the time, and mainly with the temperature achieving 93.8% of yield toward deoxygenated products with 100% of BF conversion at 320 °C. However, the catalyst activity is lost through reuse cycles, likely due to the deposition of high molecular weight compounds (coke) on the catalyst surface.
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•Nickel-molybdenum carbide (Ni- β-Mo2C) were prepared inside carbon nanotubes.•The synergistic interaction Ni - β-Mo2C reached the maximum at a Ni/Mo ratio of 0.3.•Carbon nanotubes limit the size of the inner Ni-Mo2C particles.•Ni-Mo2C particles inside CNTs showed higher activity than unsupported Ni-Mo2C.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The rs619586 polymorphism has been shown to alter the expression of MALAT1, which act as a competing endogenous RNA (ceRNA) against miR‐145. And miR‐145 was found to target COL5A1, the interaction ...between which was shown to be involved in the pathogenesis of invasive meningioma. In this study, we aimed to explore the effect of rs619586 polymorphism and its underlying molecular mechanism in invasive meningioma. Real‐time PCR and Western Blot analysis were used to study the differentiated expression of miR‐145, MALAT1 (metastasis‐associated lung adenocarcinoma transcript 1) and COL5A1 (collagen alpha‐1(V) chain) in tumour/serum samples genotyped as rs619586 AA, AG and GG. Computational analysis and luciferase reporter assay were also conducted to identify the regulatory relationship between miR‐145 and MALAT1/COL5A1. Meanwhile, expression of miR‐145 and COL5A1 in different cell treatment groups was measured to validate the results obtained from earlier experiments. As shown by the results and in tumour/serum samples genotyped as AA, AG and GG, the expression of both MALAT1 and COL5A1 was down‐regulated in a stepwise fashion, while the expression of miR‐145 was increased, suggesting a potential negative relationship between MALAT1/COL5A1 and miR‐145. Meanwhile, miR‐145 was shown to bind to MALAT1, while COL5A1 was identified as a virtual target gene of miR‐145. As a consequence, a MALAT1/miR‐145/COL5A1 molecular pathway was established based on the above results. In particular, with the presence of rs619586 A>G polymorphism, the expression of MALAT1 and COL5A1 was both reduced, leading to reduced invasiveness of meningioma.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
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