Considering the ever‐growing climatic degeneration, sustainable and renewable energy sources are needed to be effectively integrated into the grid through large‐scale electrochemical energy storage ...and conversion (EESC) technologies. With regard to their competent benefit in cost and sustainable supply of resource, room‐temperature sodium‐ion batteries (SIBs) have shown great promise in EESC, triumphing over other battery systems on the market. As one of the most fascinating cathode materials due to the simple synthesis process, large specific capacity, and high ionic conductivity, Na‐based layered transition metal oxide cathodes commonly suffer from the sluggish kinetics, multiphase evolution, poor air stability, and insufficient comprehensive performance, restricting their commercialization application. Here, this review summarizes the recent advances in layered oxide cathode materials for SIBs through different optimal structure modulation technologies, with an emphasis placed on strategies to boost Na+ kinetics and reduce the irreversible phase transition as well as enhance the store stability. Meanwhile, a thorough and in‐depth systematical investigation of the structure–function–property relationship is also discussed, and the challenges as well as opportunities for practical application electrode materials are sketched. The insights brought forward in this review can be considered as a guide for SIBs in next‐generation EESC.
The recent research progress of structure modulation technology on layered transition metal oxide cathodes for sodium‐ion batteries is summarized, concentrating especially on morphology design, coating technology, phase transition, ordering‐disordering, air stability, and composite structure to boost Na+ kinetics, suppress the irreversible phase transition, enhance the storage stability, improve the overall performance, and further realize sodium‐ion battery commercialization for market applications.
Natural killer (NK) cells play a critical role in the innate antitumor immune response. Recently, NK cell dysfunction has been verified in various malignant tumors, including hepatocellular carcinoma ...(HCC). However, the molecular biological mechanisms of NK cell dysfunction in human HCC are still obscure.
The expression of circular ubiquitin-like with PHD and ring finger domain 1 RNA (circUHRF1) in HCC tissues, exosomes, and cell lines was detected by qRT-PCR. Exosomes were isolated from the culture medium of HCC cells and plasma of HCC patients using an ultracentrifugation method and the ExoQuick Exosome Precipitation Solution kit and then characterized by transmission electronic microscopy, NanoSight and western blotting. The role of circUHRF1 in NK cell dysfunction was assessed by ELISA. In vivo circRNA precipitation, RNA immunoprecipitation, and luciferase reporter assays were performed to explore the molecular mechanisms of circUHRF1 in NK cells. In a retrospective study, the clinical characteristics and prognostic significance of circUHRF1 were determined in HCC tissues.
Here, we report that the expression of circUHRF1 is higher in human HCC tissues than in matched adjacent nontumor tissues. Increased levels of circUHRF1 indicate poor clinical prognosis and NK cell dysfunction in patients with HCC. In HCC patient plasma, circUHRF1 is predominantly secreted by HCC cells in an exosomal manner, and circUHRF1 inhibits NK cell-derived IFN-γ and TNF-α secretion. A high level of plasma exosomal circUHRF1 is associated with a decreased NK cell proportion and decreased NK cell tumor infiltration. Moreover, circUHRF1 inhibits NK cell function by upregulating the expression of TIM-3 via degradation of miR-449c-5p. Finally, we show that circUHRF1 may drive resistance to anti-PD1 immunotherapy in HCC patients.
Exosomal circUHRF1 is predominantly secreted by HCC cells and contributes to immunosuppression by inducing NK cell dysfunction in HCC. CircUHRF1 may drive resistance to anti-PD1 immunotherapy, providing a potential therapeutic strategy for patients with HCC.
As one of the most promising cathodes for rechargeable sodium‐ion batteries (SIBs), O3‐type layered transition metal oxides commonly suffer from inevitably complicated phase transitions and sluggish ...kinetics. Here, a NaLi0.05Ni0.3Mn0.5Cu0.1Mg0.05O2 cathode material with the exposed {010} active facets by multiple‐layer oriented stacking nanosheets is presented. Owing to reasonable geometrical structure design and chemical substitution, the electrode delivers outstanding rate performance (71.8 mAh g−1 and 16.9 kW kg−1 at 50C), remarkable cycling stability (91.9% capacity retention after 600 cycles at 5C), and excellent compatibility with hard carbon anode. Based on the combined analyses of cyclic voltammograms, ex situ X‐ray absorption spectroscopy, and operando X‐ray diffraction, the reaction mechanisms behind the superior electrochemical performance are clearly articulated. Surprisingly, Ni2+/Ni3+ and Cu2+/Cu3+ redox couples are simultaneously involved in the charge compensation with a highly reversible O3–P3 phase transition during charge/discharge process and the Na+ storage is governed by a capacitive mechanism via quantitative kinetics analysis. This optimal bifunctional regulation strategy may offer new insights into the rational design of high‐performance cathode materials for SIBs.
An O3‐type NaLi0.05Ni0.3Mn0.5Cu0.1Mg0.05O2 cathode material with exposed {010} active facets by multiple‐layer oriented stacking nanosheets is successfully constructed via reasonable structure design and chemical substitution. An optimal bifunctional regulation is demonstrated to be an efficient strategy to restrain the unfavorable multiphase transformation and greatly improve Na+ transport kinetics resulting in excellent performance for sodium‐ion batteries.
As one of the most promising cathode candidates for room‐temperature sodium‐ion batteries (SIBs), P2‐type layered oxides face the challenge of simultaneously realizing high‐rate performance while ...achieving long cycle life. Here, a stable Na2/3Ni1/6Mn2/3Cu1/9Mg1/18O2 cathode material is proposed that consists of multiple‐layer oriented stacking nanoflakes, in which the nickel sites are partially substituted by copper and magnesium, a characteristic of the material that is confirmed by multiscale scanning transmission electron microscopy and electron energy loss spectroscopy techniques. Owing to the optimal morphology structure modulation and chemical element substitution strategy, the electrode displays remarkable rate performance (73% capacity retention at 30C compared to 0.5C) and outstanding cycling stability in Na half‐cell system couple with unprecedented full battery performance. The underlying thermal stability, phase stability, and Na+ storage mechanisms are clearly elucidated through the systematical characterizations of electrochemical behaviors, in situ X‐ray diffraction at different temperatures, and operando X‐ray diffraction upon Na+ deintercalation/intercalation. Surprisingly, a quasi‐solid‐solution reaction is switched to an absolute solid‐solution reaction and a capacitive Na+ storage mechanism is demonstrated via quantitative electrochemical kinetics calculation during charge/discharge process. Such a simple and effective strategy might reveal a new avenue into the rational design of excellent rate capability and long cycle stability cathode materials for practical SIBs.
A stable copper and magnesium cosubstituted Na2/3Ni1/6Mn2/3Cu1/9Mg1/18O2 cathode material consisting of multiple‐layer oriented stacking nanoflakes is reported. An optimal structure design and a chemical element substitution strategy are demonstrated to greatly improve Na+ transport kinetics and structural stability of P2‐type cathode material, resulting in high‐rate and long cycle life for a sodium‐ion battery.
Improving the stability of lead halide perovskite quantum dots (QDs) in a system containing water is the key for their practical application in artificial photosynthesis. Herein, we encapsulate ...low‐cost CH3NH3PbI3 (MAPbI3) perovskite QDs in the pores of earth‐abundant Fe‐porphyrin based metal organic framework (MOF) PCN‐221(Fex) by a sequential deposition route, to construct a series of composite photocatalysts of MAPbI3@PCN‐221(Fex) (x=0–1). Protected by the MOF the composite photocatalysts exhibit much improved stability in reaction systems containing water. The close contact of QDs to the Fe catalytic site in the MOF, allows the photogenerated electrons in the QDs to transfer rapidly the Fe catalytic sites to enhance the photocatalytic activity for CO2 reduction. Using water as an electron source, MAPbI3@PCN‐221(Fe0.2) exhibits a record‐high total yield of 1559 μmol g−1 for photocatalytic CO2 reduction to CO (34 %) and CH4 (66 %), 38 times higher than that of PCN‐221(Fe0.2) in the absence of perovskite QDs.
Pores and dots: CH3NH3PbI3 (MAPbI3) perovskite quantum dots were encapsulated in the pores of iron‐porphyrin derived metal–organic frameworks (MOFs) of PCN‐221(Fex) to give an efficient photocatalytic system, which has significantly enhanced catalytic efficiency and stability for visible‐light‐driven CO2 reduction using water as an electron source.
Delivery of high‐energy density with long cycle life is facing a severe challenge in developing cathode materials for rechargeable sodium‐ion batteries (SIBs). Here a composite Na0.6MnO2 with ...layered–tunnel structure combining intergrowth morphology of nanoplates and nanorods for SIBs, which is clearly confirmed by micro scanning electron microscopy, high‐resolution transmission electron microscopy as well as scanning transmission electron microscopy with atomic resolution is presented. Owing to the integrated advantages of P2 layered structure with high capacity and that of the tunnel structure with excellent cycling stability and superior rate performance, the composite electrode delivers a reversible discharge capacity of 198.2 mAh g−1 at 0.2C rate, leading to a high‐energy density of 520.4 Wh kg−1. This intergrowth integration engineering strategy may modulate the physical and chemical properties in oxide cathodes and provide new perspectives on the optimal design of high‐energy density and high‐stable materials for SIBs.
A novel layered–tunnel intergrowth structure with stoichiometric Na0.6MnO2 composition is designed as a high‐performance cathode for sodium‐ion batteries (SIBs). Owing to the integrated advantages of the P2 layered structure with high capacity and that of the tunnel structure with excellent cycling stability and superior rate performance, this intergrowth cathode might be a promising cathode candidate for the large‐scale energy storage application of SIBs.
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•Biochar application involving compost additive and soil amendment is summarized.•Biochar addition can improve humification and nutrient retention of the compost.•Combined application ...of biochar with compost to soils shows better agronomic effects.•Biochar’s well performing is mainly due to its porous structure and functional groups.•Medium-long term monitoring of biochar amendment to soils remains necessary.
Large amounts of organic wastes, which pose a severe threat to the environment, can be thermally pyrolyzed to produce biochar. Biochar has many potential uses owing to its unique physicochemical properties and attracts increasing attentions. Therefore, this review focuses on the agronomic functions of biochar used as compost additives and soil amendments. As a compost additive, biochar provides multiple benefits including improving composting performance and humification process, enhancing microbial activities, reducing greenhouse gas and NH4 emissions, immobilizing heavy metals and organic pollutants. As a soil amendment, biochar shows a good performance in improving soil properties and plant growth, alleviating drought and salinity stresses, interacting with heavy metals and organic pollutants and changing their fate of being uptaken from soils to plants. Furthermore, combined application of biochar and compost shows a good performance and a high agricultural value when applied to soils. Objectively and undeniably, there are still negative or ineffective cases of biochar amendment on crop yield and heavy metal immobilization, which is worthy of further attention. The medium-long term field monitoring of biochar-specific agricultural functions, as well as the exploration of wider sources for biochar feedstocks, are still needed.
Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal ...layered‐tunnel heterostructure Na0.44Co0.1Mn0.9O2 cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs.
An abnormal layered‐tunnel heterostructure Na0.44Co0.1Mn0.9O2 cathode material induced by chemical element substitution is described. The crystal‐structure engineering strategy that was used gives an outlook into high‐performance sodium ion batteries.
Aerobic composting is a typical biochemical process of stabilization and harmlessness of organic wastes during which organic matter degrades, and then aggregates, to produce humic substances (HSs). ...HSs are a core product of—and a crucial indicator of—the maturation of compost that can be used in soil amendments. The formation of HSs is affected by the characteristics of the raw materials involved, the presence of compost additives, microbial activity, temperature, pH, the C/N ratio, moisture content, oxygen content and particle size, all of which can interact with each other. The formation of HSs is therefore complex. Moreover, it is difficult to identify definitive structures of humic acids (HAs) and fulvic acids (FAs), which are the two major components of HSs. However, HSs represent the same functional groups and structural arrangements, which helps to predict their structures. Functional groups represented by phenol and carboxylic acid groups of HAs and FAs can provide various agronomic functions, such as plant growth enhancement, water and nutrient retention, and disease suppression capacity. Overall, HSs can act as a soil amendment, fertilizer, and plant growth regulator. These functions of HSs enhance the reuse potential of organic waste compost products; however, this requires scientific control of various composting parameters and appropriate application of final products.
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•HSs are core components relative to humification after aerobic composting process.•Degradation of macromolecular compounds into precursors, then polymerization to HSs•HSs can enhance plant growth, retain water, enrich nutrient and suppress disease.•Reported functions of HSs are mainly associated with phenolic and carboxylic groups.•It has practically benefit to identify agronomic function related groups of HSs.
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