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Transition metal selenides are considered as promising anode materials for potassium-ion batteries (PIBs) due to their high theoretical capacities. However, their applications are limited by low conductivity and large volume expansion. Herein, sugar-gourd-shaped carbon nanofibers embedded with heterostructured ZnCo-Se nanocages are prepared via a facile template-engaged method combined with electrospinning and selenization process. In this hierarchical ZnCo-Se@NC/CNF, abundant phase boundaries of CoSe2/ZnSe heterostructure can promote interfacial electron transfer and chemical reactivity. The interior porous ZnCo-Se@NC nanocage structure relieves volume expansion and maintains structural integrity during K+ intercalation and deintercalation. The exterior spinning carbon nanofibers connect the granular nanocages in series, which prevents the agglomeration, shortens the electron transport distance and enhances the reaction kinetics. As a self-supporting anode material, ZnCo-Se@NC/CNF delivers a high capacity (362 mA h g-1 at 0.1 A g-1 after 100 cycles) with long-term stability (95.9% capacity retention after 1000 cycles) and shows superior reaction kinetics with high-rate K-storage. Energy level analysis and DFT calculations illustrate heterostructure facilitates the adsorption of K+ and interfacial electron transfer. The K+ storage mechanism is revealed by ex situ XRD and EIS analyses. This work opens a novel avenue in designing high-performance heterostructured anode materials with ingenious structure for PIBs.
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Metal phthalocyanine molecules with Me-N4 centers have shown promise in electrocatalytic CO2 reduction (eCO2R) for CO generation. However, iron phthalocyanine (FePc) is an exception, exhibiting negligible eCO2R activity due to a higher CO2 to *COOH conversion barrier and stronger *CO binding energy. Here, amine functional groups onto atomic-Fe-rich carbon dots (Af-Fe-CDs) are introduced via a one-step solvothermal molecule fusion approach. Af-Fe-CDs feature well-defined Fe-N4 active sites and an impressive Fe loading (up to 8.5 wt%). The synergistic effect between Fe-N4 active centers and electron-donating amine functional groups in Af-Fe-CDs yielded outstanding CO2-to-CO conversion performance. At industrial-relevant current densities exceeding 400 mA cm-2 in a flow cell, Af-Fe-CDs achieved >92% selectivity, surpassing state-of-the-art CO2-to-CO electrocatalysts. The in situ electrochemical FTIR characterization combined with theoretical calculations elucidated that Fe-N4 integration with amine functional groups in Af-Fe-CDs significantly reduced energy barriers for *COOH intermediate formation and *CO desorption, enhancing eCO2R efficiency. The proposed synergistic effect offers a promising avenue for high-efficiency catalysts with elevated atomic-metal loadings.
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Aqueous Zn metal batteries are attracting tremendous interest as promising energy storage systems due to their intrinsic safety and cost-effectiveness. Nevertheless, the reversibility of Zn metal anodes (ZMAs) is hindered by water-induced parasitic reactions and dendrite growth. Herein, a novel hydrated eutectic electrolyte (HEE) consisting of Zn(BF4)2·xH2O and sulfolane (SL) is developed to prevent the side reactions and achieve the outstanding cyclability of ZMAs. The strong coordination between Zn2+ and SL triggers the eutectic feature, enabling the low-temperature availability of HEEs. The restriction of BF4 - hydrolysis in the eutectic system can realize favorable compatibility between Zn(BF4)2-based electrolyte and ZMAs. Besides, the newly-established solvation structure with the participation of SL, H2O, and BF4 -, can induce in situ formation of desirable SEI with gradient structure consisting of B,O-rich species, ZnS, and ZnF2, to offer satisfactory protection toward ZMAs. Consequently, the HEE allows the Zn||Zn symmetric cell to cycle over 1650 h at 2 mA cm-2 and 1 mA h cm-2. Moreover, the Zn||NH4V4O10 full batteries can deliver a prolonged lifespan for 1000 cycles with a high capacity retention of 83.4%. This work represents a feasible approach toward the elaborate design of advanced electrolyte systems for next-generation batteries.
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Transition metal oxides are widely used as Fenton-like catalysts in the treatment of organic pollutants, but their synthesis usually requires a high temperature. Herein, an all-solid-state synthesis method controlled by graphene was used to prepare a double pyramid stacked CoO nano-crystal at a low temperature. The preparation temperature decreased by 200 °C (over 30% reduction) due to the introduction of graphene, largely reducing the reaction energy barrier. Interestingly, the corresponding degradation rate constants (kobs) of this graphene-supported pyramid CoO nano-crystals for organic molecules after their adsorption were over 2.5 and 35 times higher than that before adsorption and that of free CoO, respectively. This high catalytic efficiency is attributed to the adsorption of pollutants at the surface by supporting graphene layers, while free radicals activated by CoO can directly and rapidly contact and degrade them. These findings provide a new strategy to prepare low carbon-consuming transition metal oxides for highly efficient Fenton-like catalysts.
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Solid-state electrolytes (SEs) have attracted overwhelming attention as a promising alternative to traditional organic liquid electrolytes (OLEs) for high-energy-density sodium-metal batteries (SMBs), owing to their intrinsic incombustibility, wider electrochemical stability window (ESW), and better thermal stability. Among various kinds of SEs, inorganic solid-state electrolytes (ISEs) stand out because of their high ionic conductivity, excellent oxidative stability, and good mechanical strength, rendering potential utilization in safe and dendrite-free SMBs at room temperature. However, the development of Na-ion ISEs still remains challenging, that a perfect solution has yet to be achieved. Herein, we provide a comprehensive and in-depth inspection of the state-of-the-art ISEs, aiming at revealing the underlying Na+ conduction mechanisms at different length scales, and interpreting their compatibility with the Na metal anode from multiple aspects. A thorough material screening will include nearly all ISEs developed to date, i.e., oxides, chalcogenides, halides, antiperovskites, and borohydrides, followed by an overview of the modification strategies for enhancing their ionic conductivity and interfacial compatibility with Na metal, including synthesis, doping and interfacial engineering. By discussing the remaining challenges in ISE research, we propose rational and strategic perspectives that can serve as guidelines for future development of desirable ISEs and practical implementation of high-performance SMBs.
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Previous studies have reported the immunotoxicity of per- and polyfluoroalkyl substances (PFASs), but it remains a significant challenge to assess over 10,000 distinct PFASs registered in the distributed structure-searchable toxicity (DSSTox) database. We aim to reveal the mechanisms of immunotoxicity of different PFASs and hypothesize that PFAS immunotoxicity is dependent on the carbon chain length. Perfluorobutanesulfonic acid (PFBA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) representing different carbon chain lengths (4-9) at environmentally relevant levels strongly reduced the host's antibacterial ability during the zebrafish's early-life stage. Innate and adaptive immunities were both suppressed after PFAS exposures, exhibiting a significant induction of macrophages and neutrophils and expression of immune-related genes and indicators. Interestingly, the PFAS-induced immunotoxic responses were positively correlated to the carbon chain length. Moreover, PFASs activated downstream genes of the toll-like receptor (TLR), uncovering a seminal role of TLR in PFAS immunomodulatory effects. Myeloid differentiation factor 88 (MyD88) morpholino knock-down experiments and MyD88 inhibitors alleviated the immunotoxicity of PFASs. Overall, the comparative results demonstrate differences in the immunotoxic responses of PFASs due to carbon chain length in zebrafish, providing new insights into the prediction and classification of PFASs mode of toxic action based on carbon chain length.
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Ácidos Alcanesulfónicos , Fluorocarburos , Contaminantes Químicos del Agua , Animales , Pez Cebra , Carbono , Factor 88 de Diferenciación Mieloide , Fluorocarburos/toxicidadRESUMEN
Graphene oxide membranes-partially oxidized, stacked sheets of graphene-can provide ultrathin, high-flux and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution. These materials have shown potential in a variety of applications, including water desalination and purification, gas and ion separation, biosensors, proton conductors, lithium-based batteries and super-capacitors. Unlike the pores of carbon nanotube membranes, which have fixed sizes, the pores of graphene oxide membranes-that is, the interlayer spacing between graphene oxide sheets (a sheet is a single flake inside the membrane)-are of variable size. Furthermore, it is difficult to reduce the interlayer spacing sufficiently to exclude small ions and to maintain this spacing against the tendency of graphene oxide membranes to swell when immersed in aqueous solution. These challenges hinder the potential ion filtration applications of graphene oxide membranes. Here we demonstrate cationic control of the interlayer spacing of graphene oxide membranes with ångström precision using K+, Na+, Ca2+, Li+ or Mg2+ ions. Moreover, membrane spacings controlled by one type of cation can efficiently and selectively exclude other cations that have larger hydrated volumes. First-principles calculations and ultraviolet absorption spectroscopy reveal that the location of the most stable cation adsorption is where oxide groups and aromatic rings coexist. Previous density functional theory computations show that other cations (Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) should have a much stronger cation-π interaction with the graphene sheet than Na+ has, suggesting that other ions could be used to produce a wider range of interlayer spacings.
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Biocompatible materials and biocarriers have attracted great attention in biological wastewater treatment owing to their excellent performance in improving pollutant removal. Graphene-based material, a biocarrier candidate, with excellent adsorbability and conductivity was increasingly applied in anaerobic digestion due to its exceptional potential in the adsorption and electron transfer process. Nevertheless, the green approach for the formation of bio-graphene complexes and their mechanism in dye removal is limited. The aim of this study is to investigate and assess the performance of biological graphene hydrogel (BGH) formed by Shewanella putrefaciens CN32 on the removal of methyl orange (MO) and methylene blue (MB). The results showed that the formation of BGH is determined by the physicochemical characteristics of graphene oxide, including sheet size, oxidation degree, and interlayer distance. BGHs significantly increased the removal efficiency of dyes in comparison to non-graphene samples, with a 24-h removal rate of MO and MB reaching 92.9% and 91%, respectively. The synergetic mechanism of BGH on the enhanced removal rate of organic dye can be ascribed to GO's ability in accelerating extracellular electron transfer and stimulating biodegradation pathways relating to c-type cytochromes, including MtrA and MtrC. These findings provided an understanding of the relationship between graphene-based nanomaterials and Shewanella, which facilitated their future application in environmental biotechnology.
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A highly stable interface for aqueous rechargeable Zn batteries is of importance to inhibit the growth of Zn dendrites and suppress the side reactions. In this work, we have developed a stable honeycomb-like ZnO passivation protective layer on the Zn surface, which is in situ generated with the assistance of a nonionic surfactant additive (polyethylene glycol tert-octylphenyl ether, denoted as PEGTE). The ZnO passivation layer can facilitate the uniform distribution of the electric field, guiding the uniform deposition of Zn2+ and inhibit the generation of dendrites. As a result, the symmetric cell using the electrolyte with PEGTE shows an excellent performance at high areal capacity, reflected by stable cycling for over 2400 h at 5 mAh/cm2 and 1300 h at 10 mAh/cm2. The full cell paired with V2O5 demonstrates a long lifespan for more than 600 cycles at a low negative/positive capacity ratio.
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Electrocatalysts for highly efficient oxygen reduction reaction (ORR) are crucial for energy conversion and storage devices. Single-atom catalysts with maximized metal utilization and altered electronic structure are the most promising alternatives to replace current benchmark precious metals. However, the atomic level understanding of the functional role for each species at the anchoring sites is still unclear and poorly elucidated. Herein, we report Fe single atom catalysts with the sulfur and oxygen functional groups near the atomically dispersed metal centers (Fe1/NSOC) for highly efficient ORR. The Fe1/NSOC delivers a half-wave potential of 0.92â V vs. RHE, which is much better than those of commercial Pt/C (0.88â V), Fe single atoms on N-doped carbon (Fe1/NC, 0.89â V) and most reported nonprecious metal catalysts. The spectroscopic measurements reveal that the presence of sulfur group induces the formation of epoxy groups near the FeN4S2 centers, which not only modulate the electronic structure of Fe single atoms but also participate the catalytic process to improve the kinetics. The density functional theory calculations demonstrate the existence of sulfur and epoxy group engineer the charges of Fe reactive center and facilitate the reductive release of OH* (rate-limiting step), thus boosting the overall oxygen reduction efficiency.
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Water polluted by pharmaceutically active compounds (PhACs) and water-borne pathogens urgently need to develop eco-friendly and advanced water treatment techniques. This paper evaluates the potential of using calcium peroxide (CaO2), a safe and biocompatible oxidant both PhACs (thiamphenicol, florfenicol, carbamazepine, phenobarbital, and primidone) and pathogens (Escherichia coli, Staphylococcus aureus) in water. This paper evaluates the potential of using calcium peroxide (CaO2) as a safe and biocompatible oxidant to remove both PhACs (thiamphenicol, florfenicol, carbamazepine, phenobarbital, and primidone) and pathogens (Escherichia coli, Staphylococcus aureus) in water. The increased CaO2 dosage increased efficiencies of PhACs attenuation and pathogens inactivation, and both exhibited pseudo-first-order degradation kinetics (R2 > 0.90). PhACs attenuation were mainly via oxidization (H2O2, â¢OH/Oâ¢-, and O2â¢-) and alkaline hydrolysis (OH-) from CaO2. Moreover, concentrations of these reactive species and their contributions to PhACs attenuation were quantified, and mechanistic model was established and validated. Besides, possible transformation pathways of target PhACs except primidone were proposed. As for pathogen indicators, the suitable inactivation dosage of CaO2 was 0.1 g L-1. The oxidability (18-64%) and alkalinity (82-36%) generated from CaO2 played vital roles in pathogen inactivation. In addition, CaO2 at 0.01-0.1 g L-1 can be applied in remediation of SW contaminated by PhACs and pathogenic bacteria, which can degrade target PhACs with efficiencies of 21-100% under 0.01 g L-1 CaO2, and inactivate 100% of test bacteria under 0.1 g L-1 CaO2. In short, capability of CaO2 to remove target PhACs and microbial pathogens reveals its potential to be used as a representative technology for the advanced treatment of waters contaminated by organic compounds and microbial pathogens.
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Tianfenicol , Contaminantes Químicos del Agua , Carbamazepina/análisis , Escherichia coli , Peróxido de Hidrógeno , Oxidantes , Preparaciones Farmacéuticas , Primidona , Contaminantes Químicos del Agua/análisisRESUMEN
Lithium/sodium metal batteries have attracted enormous attention as promising candidates for high-energy storage devices. However, their practical applications are impeded by the growth of dendrites upon Li/Na plating. Here, we report that holey 2D N-doped TiNb2O7 (N-TNO) nanosheets with high electroactive surface area and large amounts of lithiophilic/sodiophilic sites can effectively regulate Li/Na deposition as an interfacial layer, leading to an excellent cycling stability. The N-TNO interfacial layer enables the Li||Li symmetric cell to sustain stable electrodeposition over 1000 h as well as the Na||Na cell to stably cycle for 2400 h at 1 mA cm-2 and 3 mA h cm-2 with a depth of discharge as high as 50%. The full cells of the Li/Na anodes based on the N-TNO layer paired with the LiFePO4 and NaTi2(PO4)3 cathodes, respectively, show a very stable cycling over 1000 cycles at a negative-to-positive electrode capacity (N/P) ratio up to 3.
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Histidine (His) is widely involved in the structure and function of biomolecules. Transition-metal ions, such as Zn2+ and Cu2+, widely exist in biological environments, and they are crucial to many life-sustaining physiological processes. Herein, by employing density function calculations, we theoretically show that the water affinity of His can be enhanced by the strong cation-π interaction between His and Zn2+ and Cu2+. Further, the solubility of His is experimentally demonstrated to be greatly enhanced in ZnCl2 and CuCl2 solutions. The existence of cation-π interaction is demonstrated by fluorescence, ultraviolet (UV) spectroscopy and nuclear magnetic resonance (NMR) experiments. These findings are of great importance for the bioavailability of aromatic drugs and provide new insight for understanding the physiological functions of transition metal ions.
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Cobre , Zinc , Cationes , Cobre/química , Histidina/química , Iones , Agua/química , Zinc/químicaRESUMEN
Cadmium (Cd) pollution in mining areas is the most important challenge for soil environment management in China. Assessing the actual Cd pollution risk in various mining areas and identifying the core areas requiring supervision can provide a basis for government departments and industries to carry out detailed further investigations in key areas. In this study, we collated published data on metal mine circumjacent soil contaminated by Cd in China from 2002 to 2020 to conduct a comprehensive study on soil cadmium pollution and ecological and health risks in mining areas. The temporal and spatial variations of Cd concentrations and the pollution source were investigated. Results indicated that the Cd concentration in soil was strongly associated with the types of mining area. The Cd pollution in the circumjacent soil of lead-zinc and tungsten mines with high heavy metal pollution discharging coefficient was more serious than the soil around other mines. Identification of temporal and spatial variations for soil Cd in China indicated that the high Cd concentrations were found in the central, southern, and southwestern regions of China, and the distribution of mining activities in these regions are relatively concentrated. Meanwhile, a temporal turning point in the mean soil Cd concentration occurred in these regions in 2012, which indicated that the heavy metal control management policy implemented by the government was effective. The ecological risk of soil Cd pollution around mining areas was moderate to high. Health risk assessment showed that some regions adjacent mining areas had a high non-carcinogenic risk, notably, lead-zinc and tungsten mining areas were more serious. Supervision should focus on reducing ecological risks and protecting the safety of agricultural products rather than concentrating on health risks. The research results provide a reference for the priority management of contaminated soil in mining areas.
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Metales Pesados , Contaminantes del Suelo , Cadmio/análisis , China , Monitoreo del Ambiente/métodos , Metales Pesados/análisis , Medición de Riesgo , Suelo , Contaminantes del Suelo/análisisRESUMEN
Diet is known to be one of the main sources from which human intake many environmental contaminants, for example, antibiotics. To determine the effect of dietary factors on antibiotic intake, we identified the levels of antibiotics present in the urine of the general population from two regions of Shanghai. Moreover, we assessed the amount of exposure to these substances and the health risks they posed. There were a total of 18 antibiotics, which were sorted into five categories. Based on the above, we used the Food Frequency Questionnaire (FFQ) and demographic data to evaluate the effects of food consumption and demographic factors on levels of the antibiotics in urine. The results found that food sourced from animals had a direct relation to the level of veterinary antibiotics or preferred veterinary antibiotics (VAs/PVAs) detected in urine. Those who regularly consumed, for example, meat, milk and eggs, had considerably more VAs/PVAs in their urine compared to those who didn't. These results demonstrated that animal-derived foods are the main causes of unintentional exposure to antibiotics in human. Our study, therefore, evidenced that more attention must be paid to the residues of unneeded VAs/PVAs derived from animal-sourced food.
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Alimentación Animal , Antibacterianos , Animales , China , Dieta , Humanos , Medición de RiesgoRESUMEN
Sodium metal is regarded as one of the most prospective next-generation anodes material owing to its high theoretical capacity, low redox potential, low cost, and natural abundance. Its most notable problem is the dendrite growth during Na plating/striping, which causes not only the safety concern but also the generation of inactive Na. Here, it is demonstrated that 2D carbon nanosheets embedded by bismuth nanoparticles (NPs) (denoted as BiâCNs) serve as a robust nucleation buffer layer to endow the sodium metal anodes (SMAs) with high Coulombic efficiencies (CEs) and dendrite-free deposition during long-term cycling. The embedded Bi nanoparticles significantly reduce the nucleation barrier through the "sodiophilic" Na-Bi alloy. Meanwhile, the carbon frameworks effectively circumvent the gradual failure of those Na-Bi nucleation sites. As a result, the metallic Na on the BiâCNs nucleation layer is repeatedly plated/stripped for nearly 7700 h (1287 cycles) at 3 mA h cm-2 with an average CE of 99.92%. Moreover, the Na||Na symmetric cells with the BiâCNs buffer layer are stably plated/stripped for 4000 h at 1 mA cm-2 and 1 mA h cm-2 . It is found that the cycling stability is closely related to the Na utilization of SMAs and current rate.
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2D MXene-based nanomaterials have attracted tremendous attention because of their unique physical/chemical properties and wide range of applications in energy storage, catalysis, electronics, optoelectronics, and photonics. However, MXenes and their derivatives have many inherent limitations in terms of energy storage applications. In order to further improve their performance for practical application, the nanoengineering of these 2D materials is extensively investigated. In this Review, the latest research and progress on 2D MXene-based nanostructures is introduced and discussed, focusing on their preparation methods, properties, and applications for energy storage such as lithium-ion batteries, sodium-ion batteries, lithium-sulfur batteries, and supercapacitors. Finally, the critical challenges and perspectives required to be addressed for the future development of these 2D MXene-based materials for energy storage applications are presented.
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Sodium metal anode (SMA) is one of the most favored choices for the next-generation rechargeable battery technologies owing to its low cost and natural abundance. However, the poor reversibility resulted from dendrite growth and formation of unstable solid electrolyte interphase has significantly hindered the practical application of SMAs. Herein, we report that a nucleation buffer layer comprising elaborately designed core-shell C@Sb nanoparticles (NPs) enables the homogeneous electrochemical deposition of sodium metal for long-term cycling. These C@Sb NPs can increase active sites for initial sodium nucleation through Sb-Na alloy cores and keep these cores stable through carbon shells. The assembled cells with this nucleation layer can deliver continuously repeated sodium plating/stripping cycles for nearly 6000 h at a high areal capacity of 4 mA h cm-2 with an average Coulombic efficiency 99.7%. This ingenious structure design of alloy-based nucleation agent opens up a promising avenue to stabilize sodium metal with targeted properties.
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The safety of energy storage equipment has always been a stumbling block to the development of battery, and sodium ion battery is no exception. However, as an ultimate solution, the use of non-flammable electrolyte is susceptible to the side effects, and its poor compatibility with electrode, causing failure of batteries. Here, we report a non-flammable electrolyte design to achieve high-performance sodium ion battery, which resolves the dilemma via regulating the solvation structure of electrolyte by hydrogen bonds and optimizing the electrode-electrolyte interphase. The reported non-flammable electrolyte allows stable charge-discharge cycling of both sodium vanadium phosphate@hard carbon and Prussian blue@hard carbon full pouch cell for more than 120 cycles with a capacity retention of >85 % and high cycling Coulombic efficiency (99.7 %).
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Enslaved to the large-size K-ions, the construction of suitable anode materials with superior and stable potassium-ion storage properties is a major challenge. 1T phase MoS2 possesses higher conductivity, bigger interlayer distance, and more electrochemically active sites than the 2H phase, which offers intriguing benefits for energy-related applications. In this work, the 1T/2H-phase hybrid MoS2 nanosheets are successfully anchored in the N-doped carbon nanotube hollow polyhedron (1T/2H-MoS2 /NCNHP) by a bottom-up solvothermal method. For the synthesized 1T/2H-MoS2 /NCNHP, the fewer-layer 1T/2H-MoS2 nanosheets are embedded in an N-doped carbon nanotube hollow polyhedron, with an enlarged interlayer spacing of 0.96 nm. When evaluated as anode material for potassium-ion batteries, the 1T/2H-MoS2 /NCNHP hybrid presents outstanding potassium storage performance. It delivers a high-specific capacity of 519.2 mAh g-1 at 50 mA g-1 and maintains 281.2 mAh g-1 at 1 A g-1 over 500 cycles. The good potassium-ion electrochemical performance is attributed to the rational structural design and the synergistic effect of the components. Moreover, the 1T-MoS2 nanosheet has excellent electrical conductivity and its enlarged interlayer spacing reduces the barrier for the embedding and stripping of K ions. Finally, the practical application of the 1T/2H-MoS2 /NCNHP electrode material is also evaluated by assembled K-ion full cells.